Visible light and nanoparticle catalysts produce desirable bioactive molecules
Researchers from Northwestern University have used visible light and quantum dots to perform selective intermolecular [2+2] cycloaddition reactions with very specific chemical products. This work, published recently by the journal Nature Chemistry, is the first use of a nanoparticle’s surface as a template for a light-driven reaction called a cycloaddition, a simple mechanism for making very complicated, potentially bioactive compounds.
Madrid will celebrate the 1st National Congress of Photocatalysis
The 1st National Congress of Photocatalysis will take place on November the 27th in the Institute of Engineering of Spain, a meeting of experts on urbanism, architecture, engineering, environment and public administration, in order to present and discuss the photocatalytic technologies and their contribution to life quality improvement in the cities. Photocatalysis is a process through which surfaces treated with titanium dioxide and other active materials neutralize harmful agents such as nitrogen oxides and volatile organic compounds among other pollutants. It is able to reduce the atmospheric contamination both indoors and outdoors. Spain already has a variety of photocatalytic applications, such as building facades in the Gran Vía of Madrid, and pedestrian pavement on Diagonal Avenue in Barcelona.
The Nobel Prize awards have been granted since 1901 following the guidelines of the Chemist Alfred Nobel, which he left written in his testament. Chemistry was the second subject to be awarded as mentioned in Nobel’s testament.
The awarding ceremony takes place in Stockholm every 10th of December, Alfred Nobel’s death anniversary.
The Royal Swedish Academy of Sciences has decided to award the Nobel Prize in Chemistry 2019 to John B. Goodenough, Akira Yoshino and Stanley Whittingham for the development of lithium-ion batteries. The awardees of the Chemistry award this year have set the bases of a wireless and fossil fuel-free society.
The lithium-ion battery has eased our lives allowing us to charge portable electronic devices that we own, wireless electronic devices! It has also allowed the development of electric cars with a longer distance and energy storage from renewable sources, like solar and wind, therefore, advancing towards a fossil fuel-free society.
Stanley Whittingham started investigating superconductors and discovered an extremely rich material in energy, which he used to create the cathode of a lithium-ion battery. But this cathode was partially made of metallic lithium, whose liter is reactive, so the battery was too explosive to be feasible.
John Goodenough showed that cobalt oxide with intercalated lithium ions can produce as much as four volts, an important advancement for the creation of much more powerful batteries. Akira Yoshino was the one who created the first commercially feasible lithium-ion battery using petroleum coke with Goodenough’s cathode as a base.
The other candidates were: Jennifer Doudna, Emmanuelle Charpentier and Feng Zhang, pioneers in the Crispr technique, which permits the genetic edition; Rolf Huisgen and Morten Meldal, for the development of cycloaddition reactions; Edwin Southern for inventing a laboratory technic to detect a sequence of DNA in a blood sample; Marvin Caruthers, Leroy Hood and Michael Hunkapiller, for contributions to protein and DNA sequencing and synthesis.
Physicists couple key components of quantum technologies
Throughout the world, researchers are thoroughly employed in the study of the quantum effect in the field of nanotechnology. At the University of Münster (Germany) they have discovered that, among their applications, these nanostructured dielectric materials can detect information using, instead of electricity, individual photons as sources of light. The objective is focused on the development of optical structures adapted to the wavelength of quantum emitters.
Energy Observer, the first self-sufficient boat propelled by sustainable hydrogen
The first boat running with fuel cells and producing its own hydrogen by electrolysis using renewable energy from photovoltaic cells, the Energy Observer, is travelling around the world to prove its efficiency. Its captain, Victorien Erussard, says that this 100 % sustainable boat, which is also a floating laboratory, has inspired new projects and initiatives wherever it goes. Massive hydrogen production helps lower its price and, as it is a sustainable fuel that can be produced anywhere, it could help reduce geopolitical conflicts, according to Erussard.
Reactor turns greenhouse gas into pure liquid fuel
Researchers from the Rice University have constructed a electrocatalysis reactor that recycles carbon dioxide to produce pure liquid fuel solutions using electricity. The reactor uses CO2 as its feedstock and the latest prototype produces highly purified and high concentration of formic acid, a product that by using other traditional dioxide devices would need costly and energy-intensive purification steps.
The scientists behind the invention hope it will become an efficient and profitable way to reuse the greenhouse gas and keep it out of the atmosphere.
Researchers from Stanford University create artificial catalysts inspired by living enzymes
Scientists have invented an enzyme-like catalyst made of polymers and a palladium core for chemically conversion molecules of oxygen and carbon monoxide into carbon dioxide. The reaction stops when the polymers are saturated with carbon dioxide, a strategy used by living enzymes. This discovery could lead to industrial catalysts capable of producing methanol using less energy and at a lower cost.
Artificial trees that absorb pollution and emit clean air in return
BioUrban, created by a group of Mexican researchers, is an artificial tree composed of microalgae that promotes photosynthesis and therefore reduces pollution naturally. Its metal structure resembles the shape of a tree, reaching four meters high and with a three-meter cup diameter, where the tanks are arranged with the microalgae. According to its creators, one of these devices has the capacity of 368 real trees, and its activity continues throughout the year. However, the purpose is not to replace forest biomass but to supplement it, as they can cover areas of high influx of people and hard-to-reach areas such as pedestrian crossings, transport terminals, etc. This idea arose from a German project called City Tree because pollution is today one of the leading causes of death in Mexico, as it affects about 20 million people daily. The need to alleviate this problem has led the authorities to take part in environmental standards, reaching even other countries such as Turkey, Colombia and Panama.
Synchrotron radiation based studies lead to more efficient and stable perovskite solar panels
The search of new materials for efficient and cheap solar cells production started up for years. Metal halide perovskites are the top-qualified materials of solar energy reception, with a high performance and with relatively low cost and requirements of processing. Devices based on perovskites were integrated recently in the solar cells market, but its success depends of its stability in the long term, due to the fact that perovskite materials, such as CsPbI3, remain their more efficient black shape and are functional in normal conditions. CsPbI3 use to have a yellow structure. Thus, researchers focused on how to obtain the stable state of this material in real ambient conditions, and a research team in KU Leuven (Belgium) have discovered an innovative solution of this issue and revealed that solar cell plane structure is able to stabilize thin films of black CsPbI3. Analysis where carried on ALBA Synchrotron and on ESRF synchrotron in Grenoble (France) through a non-crystalline diffraction technique (GIWAXS), that allows great resolution analysis of the materials and the understanding of the film changes in order to keep the black shape. It resulted in the conclusion that fastening and tension of the substrate are the key of optoelectronic devices design based on perovskite, and the mechanism is different from other methods that imply a chemical and morphological alteration of the material.
NEW PUBLICATION: Conjugated porous polymer based on BOPHY dyes as photocatalyst under visible light
The design and synthesis of new conjugated porous polymers based on BOPHY moiety (IEP-7 and IEP-8) which shows heterogeneous photocatalytic activity under visible light is reported. Both porous polymers are efficient photocatalysts in the selective oxidation of several sulfides into sulfoxides. The proposed mechanism is elucidated by steady state photolysis, fluorescence quenching and transient absorption spectroscopy, which follows a type I photosensitizing oxidation involving superoxide radical anion formation (O2− ). Electron transfer from the sulfide derivative to the photocatalyst singlet exited state takes place, giving rise the corresponding radical ion pairs. Back electron transfer from oxygen molecular to the reduced BOPHY moiety with recovery of the photocatalyst, led to the formation of superoxide radical anion in an exergonic process.
Indian scientists develop wonder material black gold
The NanoCat group, headed by Vivek Polshettiwar, at the Mumbai-based Tata Institute of Fundamental Research (TIFR) has developed a new material by rearranging size and gaps between gold nanoparticles. This process gives a black appearance to the material.
Due to the heterogeneity in nanoparticle size and inter-particle plasmonic coupling, this material presents new properties such as its ability to absorb the entire visible and near-infrared region of solar light. It was also able to act as a catalyst since it also has the capacity to absorb carbon dioxide and convert it to methane using solar energy.
Furthermore, scientists studied the solar energy absorption capacity of the material in water, which reached temperatures between 67 and 88 degrees Celsius. This leaves open the possibility of employing the material as a nano-heater to transform seawater into drinking water in an efficient way.
On July the 4th, Dr. Víctor de la Peña O’Shea was interviewed for the radio programme “Quien exporta… importa” from Radio Internacional station to explain the phenomenon of artificial photosynthesis, in the context of the SUNRISE european project. Do not miss this interview!
The Sunrise Stakeholder Workshop took place in Brussels last June 17-18, 2019
SUNRISE is one of six candidates for a future European large-scale research initiative. It proposes a sustainable alternative to the fossil-based, energy-intensive production of fuels and base chemicals. The needed energy will be provided by sunlight, the raw materials will be molecules abundantly available in the atmosphere, such as carbon dioxide, water and nitrogen.
The SUNRISE core group is formed by University of Leiden (NL, Prof. Huub de Groot, coordinator), UC Louvain (BE), Norwegian University of Science and Technology (NW), University of Turku (FI), Imperial College London (UK), University of Uppsala (SE), University of Warsaw (PL), the J. Heyrovsky Institute of Physical Chemistry (CZ) Jülich Forschungcentrum (DE), Fraunhofer (DE), CNR (IT), CEA (FR), EMPA (CH), EERA (EU), the IMDEA Energy Institute (Dr. Víctor de la Peña, contact node for Spain), ICIQ (ES), EMIRI (EU), Johnson Matthey (UK), Siemens (DE) and Engie (FR). Around this core group, it counts on the support of more than 100 institutions including Universities, research centres, companies, industry associations and public bodies.
The Sunrise Stakeholder Workshop, which took place in Brussels last June 17-18, served to present the current state of Sunrise’s work, favors supporters contribution to the “Priority Research Directions & Vision”, which feeds the comprehensive Science & Technology Roadmap, and engage discussions on the governance and innovation plans of the future initiative.
Dr. Fernando Fresno from the HyMAP team attended the workshop in representation of the IMDEA Energy Institute.
Better than any “who we are”- page, this video brings you the big picture of this international research initiative working to make artificial photosynthesis a reality for a sustainable future.
Check it out now! You can also get involved by becoming a supporter and follow us in our social media!
Scientific award and funding from the Ramón Areces Foundation awarded to Víctor A. de la Peña O'Shea
One of the most important challenges that we face as a society, from an environmental standpoint, is the development of technologies able to ease the effect of greenhouse gases, the main source of global warming.
It is in this spirit that Victor A. de la Peña O'Shea, leader of the Photoactivated Processes Unit (hymap.eu), was awarded with a three-year funding by the Ramón Areces Foundation. The research group, based in the Madrilenian Institute for Advanced Studies in Energy (IMDEA Energy), was selected for their work towards the long-awaited artificial photosynthesis by submitting their proposal: “Nanostructured multifunctional membranes for the production of solar fuels by artificial photosynthesis”.
The task of imitating nature, which involves the technological development capable of solving artificial photosynthesis, is not a simple matter. Green plants do this very process by using solar energy and carbon dioxide to produce their own nutrients and oxygen as a by-product. The chemical reaction combines CO2 and water and produces glucose and oxygen as a result. Moreover, it is the key valorization route of CO2 and one of the most promising strategies for energy storage and CO2 recycling using clean energy.
Thus, the main goal of the research group is the design of a photoelectro-catalytic device that affords the conversion of solar energy via the transformation of CO2 and H2O into either solar fuel or value-added products.
To start the project off, the designing of new multifunctional hybrid materials has been established as the first objective. Such type of materials will be the responsible for carrying out the involved chemical reactions. That is, since the process is of high complexity and involves photo-multi-electronic steps, the synthesised materials must be able to: absorb UV and visible light, in order to accomplish the separation of electrical charges, which will then be transported to the catalytic site accountable for achieving the chemical transformation.
Another commitment of the research group will be the in-depth characterisation of the own-synthesized materials in order to fully comprehend their functionalities. To that end, chemical, structural and optical techniques as well as theoretical will be employed. With this set-up in mind, the group search to understand the structure-activity relation, the chemical mechanisms of reaction and, as a conclusive ambition, to theorize the role of the fundamental components in the active centre.
The ultimate goal of the study is the construction of a photoelectrochemical device, also known as artificial leaf, that comprises two photoelectrodes made with the studied materials. This tandem cell will work without any external bias but the irradiation of solar light, in other words, without applying an electrical potential.
Along these lines, the Photoactivated Processes Unit at IMDEA Energy will work from one of the smallest scales of matter: the nanoscale, along new concepts in synthesis, to the macroscale, by way of state-of-the-art developments in solar reactor engineering. With the full intention of understanding both worlds so to become the efficient use of solar energy a reality.
Elena Alfonso and Mariam Barawi from the Photoactivated Process Unit attended last May (27th to 31th) the E-MRS 2019 Spring Meeting in Nice, France, in the Solar Fuel symposium, presenting two oral communications.
The title of Elena talk was: Design of tandem photoelectrochemical cells based on Cu2-xTe nanocrystals for water splitting,
and in Mariam case: Tandem photoelectrochemical cell for hydrogen evolution based on a new nanostructured dithiothiophene conjugated porous polymer.
Mariam also participated in the 5th EU-Korean Bilateral Workshop On Materials for Energy Applications, making an invited oral presentation named: Solar to fuel energy conversion through photocatalytic and photoelectrochemical cells.
XXXVII Biennial Meeting of the Spanish Royal Society of Chemistry
Alba, Carmen, Miguel, Marta and Víctor, some members of the Photoactivated Processes Unit, attended the XXXVII Biennial Meeting of the Spanish Royal Society of Chemistry (26-30 May 2019) in San Sebastian, Spain. In this congress, they had de opportunity to share their last research results with the rest of the scientific community, as well as to interchange different points of view about the main challenges characteristic of their research area. They have participated in the Light Symposium: Light controlled materials and processes, from medicine to artificial photosynthesis with poster, flash and oral communications.
FOTOFUEL Workshop: Current challenges in solar fuels production
The FOTOFUEL Workshop, organized by the FotoArt-CM and SUNRISE projects, took place in May 13-14 at IMDEA Energy Institute (Móstoles, Spain). This workshop included presentations from top European scientists and experts concerning the fundamental aspects of solar fuels obtaining by photocatalytic and photoelectrochemical processes.
London to have world-first hydrogen-powered doubledecker buses
London will have the world’s first hydrogen-powered doubledecker buses on its streets next year, as the capital steps up attempts to tackle its polluted air.
Transport for London (TfL) has ordered 20 of the buses, which cost around £500,000 each and only emit water as exhaust.
As well as cutting polluting exhaust emissions, the buses will run on green hydrogen produced via North Kent offshore wind farms, according to TfL.
The London mayor, Sadiq Khan, said: “We all have a role to play in cleaning up London’s toxic air and I’ve always said that TfL should lead from the front. We are investing a record £85m in cleaning up our bus fleet, and I am proud that London now has the largest zero-emission bus fleet in Europe.”
The buses can be refuelled far more quickly than conventional battery-electric buses can be recharged, requiring only one five-minute refill a day. They also have a longer range than battery buses and can be used on more routes.
Dr. Ignacio Villar, Dra. Mariam Barawi and M.Sc. Elena Alfonso, from the Photoactivated Processes Unit of IMDEA Energy, along with Dr. Freddy Oropeza from Eindhoven University of Technology are enjoying a stay for a week at Diamond Synchrotron Light Source. They are performing resonant Auger spectroscopy to study charge dynamics in semiconductors used as photocatalysts.
The regional research program FOTOART-CM, participated by several members of the HyMAP team and coordinated by HyMAP holder Dr. de la Peña O’Shea has been granted by the Regional Government of Madrid through the call “Programas de Actividades de I+D entre grupos de investigación de la Comunidad de Madrid en Tecnologías 2018”. The program focuses on artificial photosynthesis for the valorization of abundant feedstocks (CO2, H2, N2 and biomass) to obtain fuels and chemicals, and proposes different strategies to alleviate the current technological limitations like availability and stability of the developed materials and the efficiency of reactor and processes.
The FotoArt-CM consortium is composed of 6 research groups from IMDEA Energy, IMDEA Nanoscience, ICMM-CSIC, ICP-CSIC, IMDEA Materials and Universidad Autónoma de Madrid, together with 4 laboratories from the REDLAB network of Comunidad de Madrid, with the support of 18 entities comprising large companies, SMEs and business groups of different scopes, as well as two city councils (Madrid and Móstoles), 3 synchrotron light sources, a neutron source and the largest solar infrastructure in Europe (Plataforma Solar de Almería).
The scientific tasks will be accompanied by an exhaustive plan of activities that encompass the management of the whole program in its different branches, the management and transfer of results, the dissemination of those results to different audiences like scientists, business actors and general public, the training of early-stage researchers, and the mobility inside the consortium as well as to and from external centers.
Robotic organic synthesis to make reproducibility simple in chemistry
The Chemputer is an organic chemistry automation system, which allows chemical synthesis to be coupled with a high level of chemical programming language.
It was developed by Lee Cronin’s team at the University of Glasgow (DOI:10.1126/science.aav2211). They confirmed the autonomy of the Chempoter making three drugs, including Viagra and Nytol.
Scientists discover hydration is key to improving catalyst performance for industrial use
Scientists from University of California–Berkeley have used neutron scattering to identify the strong Brønsted acid site in a metal–organic framework (MOF) acid catalyst to improve the efficiency in the conversion of chemicals into new substances. By probing a material known as MOF-808-SO4, the team discovered molecular behaviour that causes the catalyst to become less acidic, which could slow down the catalytic process vital in making products such as plastics, fragrances, cosmetics, flame retardants and solvents.
Their findings, detailed in Nature Chemistry, are expected to help spur the development of new MOF catalysts that industry could use to improve the process of turning substances such as petroleum into C8 chemicals.
Scientist create Hydrogen Fuel from seawater and solar energy
A device designed in Stanford University is able to produce hydrogen in an effective and cheap way. This could be used in order to propel non-polluting vehicles.
Car engines propelled by hydrogen are based on the combustion of this molecule, with oxygen as a comburent agent to produce electricity and store it in batteries. These cars have the advantage of generating a non-polluting and non-detrimental water vapor residue. Nevertheless, hydrogen production methods need to upgrade, and they are expensive and polluting.
Recently, a group of researchers from Stanford University (California, US) have published a new study on Proceedings of the National Academy of Sciences (PNAS) Journal, and have demonstrated a new method of gaseous hydrogen and oxygen production from seawater and solar energy. This technique does not require purified water, which is expensive.
These researches have implemented a prototype that can cheaply produce hydrogen and could be escalated in mass production. In fact, the device is as effective as technologies that are based on purified water.
This method is based in electrolysis, a chemical reaction in which water is splitted when two electrodes, that are connected with a power supply, are submerged in water.
The problem is that this technology used to require pure water in order to avoid electrodes damages. From this fact, researchers found that it is possible to cover the anode through negative charges layers, with the aim of preventing sodium chloride adhesion, sea salt, and delaying corrosion. This protection, based on iron-nickel hydroxide recovering over a nickel sulfide layer, has increased the electrode useful life, and electric current intensity, providing a ten times more effective process.
According to the authors, this method leads to the opportunity of increasing hydrogen availability produced through solar and wind energy.
Researchers watch molecules in a light-triggered catalyst ring 'like an ensemble of bells'
An international team has used an X-ray laser at the Department of Energy's SLAC National Accelerator Laboratory to get an incredibly detailed look at what happens to the structure of a model photocatalyst when it absorbs light.
The researchers used extremely fast laser pulses to watch the structure change and see the molecules vibrating, ringing "like an ensemble of bells", says lead author Kristoffer Haldrup, a senior scientist at Technical University of Denmark (DTU). This study paves the way for deeper investigation into these processes, which could help in the design of better catalysts for splitting water into hydrogen and oxygen.
"We get to investigate the very basics of photochemistry, namely how exciting the electrons in the system leads to some very specific changes in the overall molecular structure", says Tim Brandt van Driel, a co-author from DTU who is now a scientist at Linac Coherent Light Source (LCLS, the SLAC's X-ray laser).
New iridium catalyst that reduces CO2 at atmospheric pressure and mild temperatures
A group of scientist in India have found a new iridium catalyst that can reduce CO2 into formate using glycerol, a waste product in biodiesel production, as a sustainable reducing agent. The approach is known as ‘transfer hydrogenation’ and until now, it was only possible at elevated pressures and temperatures.
2019: The International Year of the Periodic Table
The Periodic Table of Chemical Elements is one of the most significant achievements in science, capturing the essence not only of chemistry, but also of physics and biology.
It is a unique tool, enabling scientist to predict the appearance and properties of matter on the Earth and in the rest of the Universe.
2019 will be the 150th anniversary since Dmitry Mendeleev discovered the Periodic System and has been proclaimed the "International Year of the Periodic Table of Chemical Elements" (IYPT2019). Last Tuesday the Opening Ceremony of the IYPT2019 took place at the UNESCO HQ in Paris, France.
The initiative for IYPT2019 is supported by IUPAC in partnership with the International Union of Pure and Applied Physics (IUPAP), European Association for Chemical and Molecular Science (EuCheMS), the International Council for Science (ICSU), International Astronomical Union (IAU), and the International Union of History and Philosophy of Science and Technology (IUHPS). It was submitted by numerous organizations from over 50 countries around the world.
Development of an Electrochemical Sensor for the Detection of Drugs in Water
Pharmaceuticals are an important group of emerging contaminants in rivers or lakes, and even in drinking water, since they are usually not totally eliminated in sewage treatment plants. These pollutants, which show a clear risk to human health and the environment, represent a danger that requires better detection and prevention procedures.
In this context, a group of researchers from Rey Juan Carlos University have developed an electrochemical sensor, thanks to which it has been possible to analyze three of the most frequently β-blocking drugs (pindolol, acebutolol and metoprolol) in water.
Physicists aim to outdo the LHC with this wish list of particle colliders
If particle physicists get their way, new accelerators could one day scrutinize the most tantalizing subatomic particle in physics: the Higgs boson. Six years after the particle's discovery at the Large Hadron Collider, scientists are planning enormous new machines that would stretch for tens of kilometers across Europe, Japan or China.
The 2012 discovery of the subatomic particle, which reveals the origins of mass, put the finishing touch on the standard model, the overarching theory of particle physics. And it was a landmark achievement for the LHC, currently the world’s biggest accelerator.
Now, physicists want to delve further into the mysteries of the Higgs boson in the hope that it could be key to solving lingering puzzles of particle physics. “The Higgs is a very special particle,” says physicist Yifang Wang, director of the Institute of High Energy Physics in Beijing. “We believe the Higgs is the window to the future.”
Netherlands to Build First Solar Farm That Will Float in the Ocean
Netherlands is building the first solar farm on the surface of the ocean.
The project will begin with a test, a 30 square meter solar farm about nine miles off the coast of the Hague. The farm will be positioned between two existing offshore wind turbines and connected to the same cables, meaning the project will not require any additional infrastructure.
Offshore solar farms do have advantages over land-based ones. In addition to the lack of land costs, offshore panels tend to receive more sunlight due to the lack of obstacles, and the water acts as a coolant, increasing efficiency a 15 percent.
China was pioneered in this area, they have built solar farms on large lakes. But this will be the first floating solar farm built on the open sea, which could pose unique challenges.
The perspective Mechanistic View of the Main Current Issues in Photocatalytic CO2 Reduction has just been published in the Journal of Physical Chemistry Letters. This paper discusses the complex CO2 photoreduction mechanistic aspects considering state-of-the-art approaches, strategies and techniques.
New cover for the Journal of Physical Chemistry Letters
A cover designed by the HyMAP team has been published in the Journal of Physical Chemistry Letters following the publication of our article: Mechanistic View of the Main Current Issues in Photocatalytic CO2 Reduction. It features the complex mechanism of CO2 photoreduction as a jigsaw puzzle whose main pieces must be fitted through the use of relevant time-resolved and in situ characterization techniques.
7th Annual Workshop of Young Researchers of IMDEA Energy
The 7th Annual Workshop of Young Researchers took place in IMDEA Energy the 13th and 14th of December, where all the postdoctoral researchers and PhD students of the institute presented their newest work in both presentations and posters (just PhD), allowing the exchange of ideas and learning about many different sustainable energy related topics.
Ignacio presented our synchrotron work on Ambient Pressure XPS and core hole clock studies of our hybrid photocatalytic materials in the 5th Ambient Pressure XPS Congress celebrated in Berlin, 12-14th December.
NEW publication by the HyMAP team in Nature Communications!!
The article Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO2 photoreduction (Nature Communications, volume 9, article number: 4986, 2018) provides evidence of the key factors determining CO2 photoreduction activity of Ag/TiO2 using a combination of advanced in situ and time-resolved spectroscopies and theoretical calculations.
The HyMAP team took part in the Week of Science 2018, organized by the Region of Madrid between November 5th and 18th, with the workshop “Fabrication of dye solar cells”, framed in the activity “Energy for a sustainable world” organized by the IMDEA Energy Institute. In this workshop, the participant high school students fabricated by themselves dye sensitized solar cells using titanium dioxide and natural dyes.
Víctor, Mariam and Elena attended the nanoGe Fall Meeting 2018, held from the 22nd to the 26th of October in Torremolinos, Spain. They participated with an oral communication each within the Solar to Fuels symposium, which was focused on the lastest advances in photoelectrochemical and photocatalytic approaches for water splitting and CO2 reduction.
HYMAP team goes to Diamond Synchrotron Light Source
For the second time this year, some of the members of our group, Ignacio, Fernando and Elena, have been to Diamond Light Source, in the UK, to perform some NAP-XPS and NEXAFS experiments to study the Core Hole Clock effect on different semiconductors. We hope that this week of hard work will help to deepen knowledge on the mechanism of charge transport in photocatalysts.
Mariam Barawi presented her research at The Americas International Meeting on Electrochemistry and Solid State Science (AiMES 2018) held in Cancun, México
Mariam presented an oral communication at the AiMES conference. The title of the presentation was “New Hybrid Photoelectrodes Composed of TiO2 and Nanostructured Conjugated Porous Polymers for Enhanced Photocurrents in Solar Energy Conversion Cells”. AiMES is a joint conference of the 234th Meeting of The Electrochemical Society (ECS), the XXXIII Congreso de la Sociedad Mexicana de Electroquimica (SMEQ), and the 11th Meeting of the Mexico Section of the Electrochemical Society that was held between September 30th and October 4th, 2018 in Cancun, México. In this conference 2,100 abstracts were presented across 53 symposia.
The Nobel Prize in Physics 2018 was awarded “for groundbreaking inventions in the field of laser physics” with one half to Arthur Ashkin “for the optical tweezers and their application to biological systems”, the other half jointly to Gérard Mourou and Donna Strickland “for their method of generating high-intensity, ultra-short optical pulses”.
Contributions to the ALBA Synchrotron light facility activity report 2017
Congratulations to Víctor for his contributions to the ALBA activity report 2017: the publication Unraveling the Photoredox Nature Isolated Iron Active
Sites for Volatile Organic Compound Remediation - from Elucidating the Photoredox Nature of Isolated Iron Active Sites on MCM-41.
ACS Catalysis 7 (3), 1646–1654 (2017) - and the cover of the Catalysis section (see figure).
Hydrogen as an alternative to diesel and the electric car
The European Union set the target to reduce greenhouse gas emissions by 20 % by 2020 and by 40 % by 2030. Fuel cell electric vehicles (FCEV) are considered zero-emission vehicles (ZEV) as they use hydrogen and oxygen to generate electricity, emitting only water to the atmosphere. Their use would imply a reduction of 15.12 Mt of CO2 equivalent annually thanks to the estimation of 140,000 vehicles that would travel in Spain by 2030. “Nowadays, approximately 200 entities work to make these estimations see daylight with an accumulated inversion of 3,560 million euros by 2030”, said Javier Brey, CEO of the Spanish Hydrogen Association.
Pt/TiO2 and Pt/TiO2-COK-12 photocatalysts have been prepared by a deposition-precipitation method and characterized by means of X-ray diffraction (XRD), N2 adsorption isotherms, transmission electron microscopy (TEM), UV–vis diffuse reflectance spectroscopy (UV–vis DRS) and inductively coupled plasma optical emission spectrometry (ICP-OES). The photocatalytic activity of as-prepared photocatalyst was tested for the photocatalytic reduction of CO2 under UV light in a continuous flow gas-phase photoreactor. CH4 and CO were detected as major carbon products for all photocatalysts, with minor amounts of CH3OH. Carbon monoxide is the main product obtained over TiO2 regardless of the presence of COK-12 as a mesoporous support, whereas Pt leads to CO2 reduction towards CH4 formation, with a selectivity that reaches ca. 100% with optimum loading. Supporting the Pt/TiO2 catalysts on COK-12 preserves the selectivity of the reaction towards CH4 and further improves the overall activity of the Pt/TiO2 materials. After-reaction attenuated total reflection infrared spectroscopy (ATR-IR) and in-situ near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) have been employed to identify reaction intermediates and used to explain the observed selectivity trends.
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XXVII INTERNATIONAL SYMPOSIUM ON PHOTOCHEMISTRY: PHOTOIUPAC2018
Carmen, Marta and Raúl have recently attended the PhotoIUPAC 2018 conference held in Dublin, Ireland, from 8th to 13th July. Marta and Raúl presented the last results performed in the Photoactivated Processes Unit by two oral communications. Carmen showed some of her PhD investigations in a wonderful poster where many curious scientists went through it for getting interest in her topic. Fortunately, they were not alone in the conference and they had the chance to meet great people from Valencia Uni, La Rioja Uni, Nantes Uni and Cordoba (Argentina) Uni. Of course, they had many scientific discussions that derived to opportunities of new collaborations, as you can see in the picture.
24 Hour Solar Energy: Molten Salt Makes It Possible, and Prices Are Falling Fast
The image shows a 110-megawatt concentrated solar power (CSP) plant built and operated by Solar Reserve in Santa Monica, California. With this plant, they are trying to prove that the technology which drives Crescent Dunes can make solar power an affordable, carbon-free, day-and-night energy source, dispatched on the electric grid like any fossil fuel plant. In this plant, concentrated sunlight heats molten salt to 1,050 degrees Fahrenheit in the shimmering tower; then the salt gets stored in a giant insulated tank and can be tapped to make steam to run a turbine.
XXXIX Meeting of the Electrochemistry Group of the Spanish Royal Society of Chemistry
Mariam attend the XXXIX Meeting of the Electrochemistry Group of the Spanish Royal Society of Chemistry and 3rd E3 Mediterranean Symposium: Electrochemistry for Environment and Energy and she present a poster called: “Hybrid materials composed of nanostructured Conjugated Porous Polymers and TiO2 for Enhanced hydrogen evolution in Photoelectrochemical Cells”.
There, she had the opportunity to meet many electrochemists who work in Spain and exchange impressions and ideas.
The Sun-to-Liquid Summer School took place at Rey Juan Carlos University and IMDEA Energy from the 25th to the 29th of June. Fernando participated with an oral presentation and guiding a practice session, while Elena attended as a student. In this summer school, the topic of solar fuels was addressed from many different points of view; ranging from the scientific basis of photocatalytic and thermochemical syngas generation to the life cycle, techno-economic and geopolitical assessment of its production.
Carbon Engineering to commercialise CO2 capture from air
The company recently published an article in Joule that has stimulated debate on the potential of extracting CO2 directly from air. In their web page they estimate cost of $100-150 USD per ton of CO₂ captured, purified, and compressed to 150 bar.
The company is also trying to develop an Air to FuelsTM technology that uses the captured CO2 and H2 to produce fuels in a second step.
Carmen was awarded the prize for the best poster at the XXVII Biennial Meeting in Organic Chemistry (20-22 June, 2018). Her poster addresses the design and synthesis of conjugated porous polymers based on BOPHY dyes for solar fuel production.
The Single Crystal X- Ray Crystallography School took place from 18 to 22th of June organized by Chemical Synthesis and Homogeneous catalysis Institute of CSIC at the University residence of International University Menendez Pelayo-UIMP in Jaca (Huesca). The course was given by excellent researchers from different Spanish centers, without forgetting the presence of Carmelo Giacovazzo, reference worldwide in structural resolution.
Raúl, Marta and Carmen attended the XXVII Biennial Meeting in Organic Chemistry (20-22 June, 2018) last week.
Marta and Raúl both participated with oral communications about their research, and Carmen with a poster. They had the opportunity to meet other organic chemists and to exchange knowledge and ideas.
In collaboration with Benito Alcaide´s group of Complutense University of Madrid, some members of Hymap Group published the hot paper ”A Facile Synthesis of Blue Luminescent HelicenoCarbazoles Based on Gold-Catalyzed Rearrangement-Iodonium Migration and Suzuki-Miyaura Benzannulation Reactions” in Chemistry- A European Journal. This paper demonstrates the utility of gold catalysis in the preparation of advanced materials with efficient blue luminescent properties that have been elucidated by single crystal X-Ray diffraction.
2nd FOTOFUEL School on Solar Fuels held in Almería on June 4th
The second edition of the FOTOFUEL School on Solar Fuels, chaired by V. de la Peña and F. Fresno, took place last week in Almería in connection to the 10th European Meeting on Solar Chemistry and Photocatalysis (SPEA 10). The lectures by R. Navarro (ICP-CSIC), P. Fornasiero (Univ. Trieste), O. Ishitani (Tokyo Inst. of Technology), C. Gimbert-Suriñach (ICIQ), T. Andreu (IREC) and S. Giménez (Univ. Jaime I) were attended by 70 PhD students and postdocs from 23 different countries.
Carmen, Marta, Víctor and Raúl recently published the paper “Synchronized biphotonic process triggering C-C coupling catalytic Reactions” in the journal Applied Catalysis B: Environmental.
This work focuses on the study of a novel TTA-UC system and its application as a catalyst in C-C coupling reactions. Our researchers carried out several experiments in order to understand the mechanism of this kind of systems. They studied the scope of the reaction and finally they developed a continuous-flow system to scale up the reaction.
Congratulations for your nice work!
XAS measurements at UVX synchrotron light source, Brazil
Nacho and Freddy (Dr. Freddy Oropeza, a collaborator from the University of Technology in Eindhoven) just spent two weeks in the UVX synchrotron light source in Campinas, Brazil, performing XAS and core hole clock experiments on the conjugated porous polymers and TiO2/polymer hybrids materials that we are studying in the group for artificial photosynthesis. We expect to characterise the conduction band and measure electron delocalisation times of these materials that will provide us with information on their ability to separate charges and avoid electron-hole recombination.
Promising artificial photosynthesis inspired by a frog
Engineers from the University of Cincinnati have created a foam to produce artificial photosynthesis inspired by the one that the Tungara frog (Engystomops pustulosus) uses to build a protective scum nest for its eggs. This foam, unlike many natural photosynthetic systems, converts all of the captured solar energy into sugars with a yield of around 96 %. For this reason, it can be used in a very carbon-rich environment , such as coal-fired power plant discharges.
Electric vehicle infrastructure sector to gather this summer
The electric vehicle infrastructure industry will gather this summer to tackle the electrification of transport. The conference is organized by Clean Energy News’ publisher Solar Media and will be held on the 3rd and 4th of July 2018 at London’s America Square Conference Centre.
The meeting includes sessions on EV infrastructure investment plans, business model innovations, the impact on the grid and energy networks, and emerging technologies such as vehicle-to-grid battery storage.
In-situ EXAFS and NEXAFS photoelectrochemical measurements at ALBA synchrotron
Mariam, Ignacio and Elena have been to BL22-CLAESS beamline at ALBA Synchrotron Light facility in Barcelona, where they performed in-situ NEXAFS and EXAFS experiments using a novel photoelectrochemical cell designed for this purpose. With this new setup, changes on the surface of different photoelectrodes due to illumination or the application of a potential were monitored.
The 2nd Workshop on Photocatalytic Materials took place today at the Autonomous University of Madrid (UAM). It saw the participation of FRONCAT-UAM group, three IMDEA institutes (Energy, Materials and Nanoscience), the Materials Science Institute of Madrid and the Catalysis and Petrochemical Institute of Madrid.
A SPECS Near Ambient Pressure X-ray Photoemission Spectroscopy (NAP-XPS) system has arrived to IMDEA Energy Institute. It has been purchased by the HyMAP group and it will enable us to do in-situ measurements in order to elucidate the artificial photosynthesis mechanism at our facilities.
Víctor Antonio de la Peña O'Shea has been awarded the Madri+d Award to the best European Research Council (ERC) Funded Project of the Community of Madrid for the HyMAP project. The ceremony has taken place at the Royal Post Office in Puerta del Sol, headquarters of the Presidential Council of the Community of Madrid. Congratulations Víctor!
In-situ near-ambient pressure XPS and NEXAFS at Diamond Light Source
Víctor, Ignacio and Elena from HyMAP group have visited Diamond Light Source, the UK' s national synchrotron science facility, to perform in-situ near-ambient pressure XPS and NEXAFS experiments on photocatalysts samples. Spectra were acquired under different gas conditions and light illumination. Their interpretation will help to get a better understanding of photocatalytic reaction mechanisms.
NEW research and development project for our group!
Raúl and Fernando have been awarded a new research and development project, including transfer, by the Ministry of Economy, Industry and Competitiveness of Spain: Obtaining of Solar Fuels in Wide-Spectrum Photoactivated Catalytic Devices (code ENE2017-89170-R). It will have a duration of three years and it is included in the I+D+I projects (Challenges). Congratulations Raúl and Fernando!
NEW PUBLICATION! Polímeros Conjugados Porosos como fotocatalizadores para la generación de combustibles
Conjugated Porous Polymers comprising fully p-conjugated networks represent a new generation of heterogeneous photocatalyst for solar fuel production. These materials exhibit a great number of interesting properties such as semiconductor abilities, large photo- and thermo stabilities, light absorption in a wide range of solar spectrum and a huge chemical versatility in comparison with inorganic semiconductor. This mini review includes selected examples about their use as photocatalyst for artificial photosynthesis mainly in H2 evolution from water. Recent advances in the development of these polymers have shown how their textural, morphological and opto-electronic properties have a great influence in the photocatalytic behaviour; however, the relationship between these properties and the reaction mechanism is still unclear. Therefore, the design of new conjugated porous polymers as photocatalyst needs an intensive effort in the use advance “operando” characterisation and modelling to fully understand these processes. This is a very promising field in the development of multifunctional optoelectronic materials research area being one the most important challenges their applicability as photocatalyst for artificial photosynthesis by CO2 photoreduction which success will means a high environmental, energetic, social and economic impact. Revista de Plásticos Modernos, 114, 728, Noviembre 2017
6th Annual Workshop of Young Researchers of IMDEA Energy Awards
Patricia Reñones and Fernando Fresno from HyMAP group have been awarded for their outstanding scientific contributions in 2017 as predoctoral and postdoctoral researcher respectively in the 6th Annual Workshop of Young Researchers of IMDEA Energy, held in Madrid on 15th December the 2017. Congratulations!!
New photonic self-assembled metal-organic framework particles
Researchers from the Instituto de Ciencia de Materiales de Madrid (ICMM)
in collaboration with Institut Català de Nanociència i Nanotecnologia
(ICN2) have developed highly porous metal-organic particles which
spontaneously assemble in tridimensional superstructures. The band gap
of this new material can be tuned by changing the size of its particles.
This work has been published in Nature Chemistry and can be useful in a
number of fields such as catalysis.
The work on substitutions in aryl halides by means of a dichromatic photocatalytic process has been just accepted in Chemistry A European Journal. Congratulations to Víctor and Raúl. Have a look here http://onlinelibrary.wiley.com/doi/10.1002/chem.201705326/full
Hydrogen fuel cell trains will operate in Germany from 2021
LOWER Saxony Transport Authority (LNVG) signed a contract with Alstom and gas supplier Linde Group in Wolfsburg on November 9 for a fleet of 14 Coradia iLint hydrogen fuel multiple units, which will replace diesel trains on non-electrified routes in northwest Germany from 2021 onwards. The contract - the first order for the iLint - includes 30 years’ maintenance and energy supply for the fleet. Linde will install dedicated hydrogen refuelling facilities for the fleet of 140km/h trains, which will be capable of operating up to 1000km on a single tank of hydrogen.
The Unit of Photoactivated Processes took part in the Week of Science 2017, organized by the Region of Madrid between November 6th and 19th, with the workshop “Solar fuels and photocatalysis”, framed in the activity “Energy for a sustainable world” organized by the IMDEA Energy Institute. In this workshop, the participant high school students attended a speech about the relevance of solar fuels and the related activities developed in this field in the frame of HyMAP. In addition, they could realize themselves a simple experiment about the relationships among light, colour and oxidation states.
Our colleague, Marta Liras, senior researcher of the photoactivated processes unit, presents the science week of madrid 2017
Learn fundamental concepts of physics through superheroes stories, learn about nanotechnology, discover how water supply works from the "El Atazar" reservoir, or didactic workshops for children to understand the process of artificial photosynthesis, are some of the activities programmed by the Community of Madrid, through the madri + d Foundation, in the 17th edition of the Science Week, which will take place from November 6 to 19 in more than 50 municipalities of the region.
This initiative aims to encourage the participation of citizens in the scientific world, especially among children and young people, encourage vocations and entrepreneurship among students and show the immense scientific and technical heritage of the region.
NEW PUBLICATION! A new pathway for protein haptenation by β-lactams
The covalent binding of β-lactams to proteins upon photochemical activation has been demonstrated by using an integrated approach that combines photochemical, proteomic and computational studies, selecting human serum albumin (HSA) as a target protein and ezetimibe (1) as a probe. The results have revealed a novel protein haptenation pathway for this family of drugs that is an alternative to the known nucleophilic ring opening of β-lactams by the free amino group of lysine residues. Thus, photochemical ring splitting of the β-lactam ring, following a formal retro-Staudinger reaction, gives a highly reactive ketene intermediate that is trapped by the neighbouring lysine residues, leading to an amide adduct. For the investigated 1/HSA system, covalent modification of residues Lys414 and Lys525, which are located in sub-domains IIIA and IIIB, respectively, occurs. The observed photobinding may constitute the key step in the sequence of events leading to photoallergy. Docking and molecular dynamics simulation studies provide an insight into the molecular basis of the selectivity of 1 for these HSA sub-domains and the covalent modification mechanism. Computational studies also reveal positive cooperative binding of sub-domain IIIB that explains the experimentally observed modification of Lys414, which is located in a barely accessible pocket (sub-domain IIIA).
NEW PUBLICATION! Addressed realization of multication complex arrangements in metal-organic frameworks
The preparation of materials with structures composed of multiple metal cations that occupy specific sites is challenging owing to the difficulty of simultaneously addressing the incorporation of different elements at desired precise positions. We report how it is possible to use a metal-organic framework (MOF) built with a rod-shaped inorganic secondary building unit (SBU) to combine multiple metal elements at specific positions in a manner that is controllable at atomic and mesoscopic scales. Through the combination of four different metal elements at judiciously selected molar ratios, 20 MOFs of different compositions and the same topology have been prepared and characterized. The use of diffraction techniques, supported by density functional theory calculations, has led us to determine various possible atomic arrangements of the metal cations within the SBUs. In addition, seven of the compounds combine multiple types of atomic arrangements, which are mesoscopically distributed along the crystals. Given the large diversity and importance of rod-based MOFs, we believe that these findings offer a new general strategy to produce complex materials with required compositions and controllable arrangements of the metal cations for desired applications.
Castillo-Blas et al., Sci. Adv. 2017;3:e1700773
New publication! QDs decorated with thiol-monomer ligands as new multicrosslinkers for the synthesis of smart luminiscent nanogels and hydrogels
Herein, new smart thermo-responsive photoluminescent nano- and macrogel hybrids based on quantum dots (QDs) and poly(diethylene glycol methyl ether methacrylate) (pMEO2MA) are reported. The synthetic strategy comprises the functionalization of the homemade hydrophobic CdSe nanoparticles (NPs) with thiol-functionalized methacrylic monomers via ligand exchange reactions. Therefore, the organic–inorganic hybrid QD NPs decorated with methacrylic groups are able to connect the inorganic core with the growing pMEO2MA chains during the radical polymerization reaction by acting as multicrosslinker nanoagents. Depending on whether the bottom-up polymerization approach is conducted in solution or in bulk, nanometric core–shell QD@pMEO2MA NPs or hybrid pMEO2MA hydrogels crosslinked by QD NPs are achieved, respectively. Both nanogel and hydrogel hybrids experience a considerable and sudden increase in the fluorescence emission upon heating due to gel collapse at the volume phase transition temperature (VPTT), independent of pH. Moreover, at very basic pH (pH 12), the hydrogels also undergo a colour change from red to fully blue, which makes them promising as pH sensors. Both pH- and thermo-response are reversible in both nano- and macro-gel materials. Polym. Chem., 2017, 8, 5317
DIPC School on PhotoElectroCatalysis at the Atomic Scale (PECAS)
Ignacio, Elena and Mariam attended the Donostia International Physics Center (DIPC) School on PhotoElectroCatalysis at the Atomic Scale (PECAS), which took place in Donostia-San Sebastián, Basque Country (Spain), from June 27th to 30th, 2017.
The school aimed at promoting interdisciplinary discussion of scientists in the material science and photoelectrochemistry fields in addition to presentation of new results, ideas and methods to understand the catalyst-electrolyte interface at an atomic level.
NEW PUBLICATION! Visible-Light Photocatalytic Intramolecular Cyclopropane Ring Expansion
Described herein is a new visible-light photocatalytic strategy for the synthesis of enantioenriched dihydrofurans and cyclopentenes by an intramolecular nitro cyclopropane ring expansion reaction. Mechanistic studies and DFT calculations are used to elucidate the key factors in this new ring expansion reaction, and the need for the nitro group on the cyclopropane. Angew. Chem. 2017, 129, 7934-7938
The 1st Workshop UAM-FRONCAT and IMDEA Energy-PHOTPRO 2nd-June, IMDEA Energy will take place on Friday 2ndst June at the premises of IMDEA Energy Institute to stablish contact and promote collaborations between the Frontiers in Catalysis (FRONCAT) group at UAM and the Photoactivated Processes Group at IMDEA Energy.
New publication! Effect of La as Promoter in the Photoreduction of CO2 Over TiO2 Catalysts
In this work, TiO2 has been modified by treating it thermally together with different proportions (0.5–15 wt%) of La2O3. The resulting materials have been extensively characterized by XRD, TEM, N2 adsorption isotherms, temperature-programmed CO2 desorption, Raman, UV–VIS photoluminescence and X-Ray Photoelectron spectroscopies. The activity tests of these materials for the gas-phase photocatalytic reduction of carbon dioxide show that the main products of the reaction are in all cases CO and CH4, together with H2 from the parallel reduction of water. After the preparation procedure, La phases are best described as oxycarbonates, and lead to improved activity with respect to TiO2 with La contents up to 5 wt%. Higher loadings do not, however, lead to further enhanced activity. Retarded electron–hole recombination and enhanced CO2 adsorption are invoked as the key factors contributing to this activity improvement, which is optimized in the case of 0.5 wt% La leading to higher productions of CO and CH4 and increased quantum efficiency with respect to titania.
LECTURE: "Light-Matter Interaction: Evolution towards a Green Photochemistry"
Raúl Pérez was invited to teach a master´s lecture on the "Química Sostenible y Catálisis" topic in the "Master en Química Molecular y Catálisis Homogénea" at the Instituto de Síntesis Química y Catálisis Homogénea (CSIC-Universidad de Zaragoza, Spain).
New Mariam´s publication! Electronics and optoelectronics of quasi-1D layered transition metal trichalcogenides
The isolation of graphene and transition metal dichalcongenides has opened a veritable world to a great number of layered materials which can be exfoliated, manipulated, and stacked or combined at will. With continued explorations expanding to include other layered materials with unique attributes, it is becoming clear that no one material will fill all the post-silicon era requirements. Here we review the properties and applications of layered, quasi-1D transition metal trichalcogenides (TMTCs) as novel materials for next generation electronics and optoelectronics. The TMTCs present a unique chain-like structure which gives the materials their quasi-1D properties such as high anisotropy ratios in conductivity and linear dichroism. The range of band gaps spanned by this class of materials (0.2 eV–2 eV) makes them suitable for a wide variety of applications including field-effect transistors, infrared, visible and ultraviolet photodetectors, and unique applications related to their anisotropic properties which opens another degree of freedom in the development of next generation electronics. In this review we survey the historical development of these remarkable materials with an emphasis on the recent activity generated by the isolation and characterization of atomically thin titanium trisulfide (TiS3).
New publication! Cyclohexanedione as negative electrode reaction for aqueous organic redox flow batteries
The electrochemical reduction and oxidation of cyclohexanedione is evaluated for the first time as the negative electrode reaction in an organic redox flow battery. Electrochemical characterization indicates that the redox reaction of cyclohexanedione is a proton-coupled electron transfer process with quasi-reversible behavior in acidic media (pH < 3). Among three isomeric compounds (1,2-, 1,3- and 1,4-cyclohexanedione), the reduction of 1,3-cyclohexanedione exhibits the most negative electrode potential (c.a. −0.6 V vs. Ag|AgCl (c.a. −0.4 V vs. NHE)) as well as the widest pH operating range (pH 1–5) for relatively reversible reactions. The resulting electrode potential is the most negative of those to have been reported in neutral/acidic electrolytes. 1,3-cyclohexanedione is subsequently used as the active species in the negative electrode of a parallel plate flow cell, which is charge-discharge cycled at 3.4 mA cm−2 for 100 cycles, yielding half-cell coulombic efficiencies of c.a. 99%. The organic molecules derived from this group are observed to have high solubilities (>2 M) and exhibit reduction process with up to 4 electrons transferred.
NEW PUBLICATION: Upconversion nanoparticles with a strong acid-resistant capping
Water-dispersible upconversion nanoparticles (beta-NaYFCO4:YbCO3+,Er3+, UCNP) coated with a thin shell of a biocompatible copolymer comprising 2-hydroxyethylmethacrylate (HEMA) and 2-acrylamido-2-methyl-1-propanesulphonsulphonic acid (AMPS), which we will term COP, have been prepared by multidentate grafting. This capping is remarkably resistant to strong acidic conditions as low as pH 2. The additional functionality of the smart UCNP@COP nanosystem has been proved by its association to a well-known photosensitizer (namely, methylene blue, MB). The green-to-red emission ratio of the UC@COP@MB nanohybrid exhibits excellent linear dependence in the 7 to 2 pH range as a consequence of the release of the dye as the pH decreases.
Marta Liras receives the prestigious Ramon y Cajal award
Marta Liras has been the recipient of one of the prestigious Ramón y Cajal award which will fund her project: “Design and Synthesisof Hybrid Materials for Advances Applications: Solar FuelsGeneration” (RYC - 2015 - 18677). The funding is provided by the Ministry of Economy, Industry and Competitiveness for the period: 2017-2021.
NEW PUBLICATION: Elucidating the Photoredox Nature of Isolated Iron Active Sites on MCM-41
Photocatalytic performance is highly dependent on the nature and dispersion of the active sites, playing a crucial role in the optoelectronic and charge-transfer processes. Here, we report stabilized isolated iron on MCM-41 as a highly active catalyst for a photoredox reaction. The unique nature of the single-atom centers exhibit a trichloroethylene conversion per iron site that is almost 5 times higher than that of TiO2. Advanced characterization and theoretical calculations indicate the generation of hydroxyl radicals, through a photoinduced ligand-to-metal charge-transfer mechanism, which act as hole scavengers that lead to the formation of intermediate oxo–iron species (Fe-O). This intermediate species is the key step in promoting the photocatalytic reactions. Understanding the mechanistic photoredox pathway in isolated active site materials is imperative for developing highly efficient nonprecious photocatalysts for environmental or energy applications.
The group welcomes Mariam Barawi, a new postdoctoral researcher in the group who will be working on the development of photoelectrochemical cells for solar fuel production (CO2 reduction and H2 evolution reaction).
CO2 reduction over NaNbO3 and NaTaO2 perovskite photocatalysts
The activity of NaNbO3 and NaTaO3 perovskites for the photocatalytic reduction of CO2 is studied in this work. For this purpose, sodium niobate and tantalate have been prepared using solid-state reactions, extensively characterised by means of powder X-ray diffraction, UV-vis, photoluminescence and Raman spectroscopies and N2 adsorption isotherms, and tested in the gas-phase reduction of CO2 under UV light in a continuous flow photoreactor. NaNbO3 is constituted of an orthorhombically distorted perovskite structure, while a ca. 4.5:1 combination of the orthorhombic and monoclinic modifications is found in the tantalate. Both catalysts exhibit interesting intrinsic activities, with the tantalate material giving rise to a slightly higher performance. This is attributed to a compromise situation between electron–hole recombination and the reducing potential of conduction band electrons. In addition, a decrease in the competition of water protons for photogenerated electrons is observed with both catalysts with respect to TiO2.
NEW PUBLICATION: A deprotection strategy of a BODIPY conjugated porous polymer to obtain a heterogeneous (dipyrrin)(bipyridine)ruthenium(II) visible light photocatalyst
This work shows that a deprotection strategy of BODIPY conjugated porous polymers (CMPBDPs) can be successfully applied to synthesize a new (dipyrrin)(bipyridine)Ru(II) (CMPBDP-Ru) efficient heterogeneous photocatalyst for iminium ion generation under visible light. CMPBDP-Ru shows high thermal and photochemical stability under irradiation, and it could be reused several times.
Conference organisation: 1st FOTOFUEL School & Conference
Fernando Fresno, Víctor A. de la Peña O´Shea, Marta Liras, Carmen García, Alba García and Patricia Reñones are part of the organising commitee of the 1st FOTOFUEL School & Conference which is being organised in Almería Spain until 27th October in collaboration with PSA.
GROUP CONTRIBUTIONS AT THE 1st FOTOFUEL School & Conference
Patricia Reñones, Fernando Fresno, Alba García-Sánchez, Carmen García, Marta Liras, Víctor A. de la Peña O’Shea presented their work at the 1st FOTOFUEL School & Conference that it is being held in Almería, Spain this week.
ORAL COMMUNICATION: New insight in Artificial Photosynthesis: from inorganic semiconductors to hybrid multifunctional materials
Víctor A. de la Peña O´Shea presented the talk: "New insight in Artificial Photosynthesis: from inorganic semiconductors to hybrid multifunctional materials" in the 6th EUCHEMS Chemistry Congress in Seville, Spain by authors: M. Liras; A. García; P. Reñones; F. Fresno; Víctor A. de la Peña O´Shea.
ORAL COMMUNICATION: Conjugated microporous polymer based on dithienothiophene moieties and TiO2 hybrid materials as CO2 photoreduction catalyst
Marta Liras presented the talk: "Conjugated microporous polymer based on dithienothiophene moieties and TiO2 hybrid materials as CO2 photoreductioncatalyst" in the 6th EUCHEMS Chemistry Congress in Seville, Spain by authors: M. Liras; A. García; P. Reñones; F. Fresno; V. A. de la Peña O´Shea.
ORAL COMMUNICATION: Photoreduction of CO2 using hybrid heterojuntion photocatalysts
Víctor A. de la Peña O’Shea presented the talk: "Photoreduction of CO2 using hybrid heterojuntion photocatalysts" in the Catalysis for Clean Energy and Sustainable Chemistry (CCESC 2016) in Madrid, Spain by authors: Strasbourg, France by authors: Patricia Reñones, Fernando Fresno, Laura Collado, Alba García-Sánchez, Marta Liras, Víctor A. de la Peña O’Shea.
ORAL COMMUNICATION: Conjugated microporous polymer based on dithienothiophene moieties and TiO2 hybrid materials as CO2 photoreductioncatalyst
Marta Liras presented the talk: "Conjugated microporous polymer based on dithienothiophene moieties and TiO2 hybrid materials as CO2 photoreductioncatalyst" in the Vth Iberian Photochemistry Congress in Toledo, Spain by authors: M. Liras; A. García; P. Reñones; F. Fresno; V. A. de la Peña O´Shea.
NEW PUBLICATION: Ga-Promoted Photocatalytic H2 Production over Pt/ZnO Nanostructures
Photocatalytic H2 generation is investigated over a series of Ga-modified ZnO photocatalysts that were prepared by hydrothermal methods. It is found that the structural, textural, and optoelectronic properties remarkably depend on the Ga content. The photocatalytic activity is higher in samples with Ga content equal to or lower than 5.4 wt %, which are constituted by Zn1–xGaxO phases. Structural, textural, and optoelectronic characterization, combined with theoretical calculations, reveals the effect of Ga in the doped ZnO structures. Higher Ga incorporation leads to the formation of an additional ZnGa2O4 phase with spinel structure. The presence of such a phase is detrimental for the textural and optoelectronic properties of the photocatalysts, leading to a decrease in H2 production. When Pt is used as the cocatalyst, there is an increase of 1 order of magnitude in the activity with respect to the bare photocatalysts. This is a result of Pt acting as an electron scavenger, decreasing the electron–hole recombination rate and boosting the H2 evolution reaction
NEW PUBLICATION: Photocatalytic H2 production from aqueous methanol solutions using metal-co-catalysed Zn2SnO4 nanostructures
The activity of nanocrystalline Zn2SnO4 for photocatalytic hydrogen production from methanol aqueous solutions has been explored. A co-precipitation method starting from metal salts and a mild base as precipitating agent was used to obtain highly crystalline nanosized Zn2SnO4 with cubic inverse spinel structure. In-situ photodeposition of Pt and Au nanoparticles as co-catalysts was performed prior to the photocatalytic reaction. The obtained materials have been characterised by XRD, TEM, N2 adsorption isotherms and ICP-OES, Raman, UV–vis and photoluminescence spectroscopies. Bare Zn2SnO4 gives rise to hydrogen release from a methanol aqueous solution without catalyst deactivation. This photocatalytic activity is remarkably increased with the deposition of platinum. In contrast, the use of gold as co-catalyst increases the activity only slightly, with a lower hydrogen production than a Pt-loaded sample with the same nominal metal content. An improved charge separation and the activity of Pt as hydrogen evolution catalyst are invoked to account for the present findings.
Poster presentation: An Excellence Network Facing the New Challenges in Artificial Photosynthesis
Víctor A. de la Peña O´Shea presented the poster: "An Excellence Network Facing the New Challenges in Artificial Photosynthesis" in the 21st International Conference on Photochemical Conversion and Storage of Solar Energy in St. Petersburg, Russia by authors: : V. A. de la Peña O’Shea, F. Fresno, J. L. G. Fierro, A. Llobet, H. García, J. J. Vilatela, M. A. García-Aranda, F. Illas, S. Giménez, S. Malato.
Oral Communication: New insight into solar fuels production by artificial photosynthesis
Víctor A. de la Peña O´Shea presented the talk: "New insight into solar fuels production by artificial photosynthesis " in the 21st International Conference on Photochemical Conversion and Storage of Solar Energy in St. Petersburg, Russia by authors: L. Collado, P. Reñones, A. García-Sánchez, M. Liras, F. Fresno, V.A. de la Peña O`Shea.
POSTER PRESENTATION: FOTOREDUCCIÓN DE CO2 POR MEDIO DE CATALIZADORES HÍBRIDOS
Patricia Reñones presented the poster: "Fotoreducción de CO2 por Medio de catalizadores híbridos" in the "II Encuentro Jóvenes Investigadores de la SECAT" Ciudad Real, Spain by authors: P. Reñones, F. Fresno, A. García, M. Liras, L. Collado, V. A. de la Peña O’Shea
POSTER PRESENTATION: Synthesis of multifunctional Hybrid Materials: in the way to Artificial Photosynthesis
Alba García presented the poster: "Synthesis of multifunctional Hybrid Materials: in the way to Artificial Photosynthesis" in the "Valorización química sostenible de CO2" Congress in Santander, Spain, by authors: A. García, P. Reñones, F. Fresno, M. Liras, V. A. de la Peña O’Shea.
WORKSHOP: Las tecnologías CAC: una oportunidad en la mitigación del cambio climático
Víctor A. de la Peña O´Shea participated in the workshop: “Las tecnologías CAC: una oportunidad en la mitigación del cambio climático” organised by the “Plataforma Tecnológica Española del CO2 (PTECO2)” network in Zaragoza, Spain.
WORKSHOP: Captura y usos del CO2: un camino hacia la sostenibilidad
Víctor A. de la Peña O´Shea participated in the workshop: “Captura y usos del CO2: un camino hacia la sostenibilidad” organised by the “Plataforma Tecnológica Española del CO2 (PTECO2)” network in Bilbao, Spain.
POSTER PRESENTATION: An Excellence Network Facing the New Challenges in Artificial Photosynthesis
Fernando Fresno presented the talk: "An Excellence Network Facing the New Challenges in Artificial Photosynthesis" in the 9th European meeting on Solar Chemistry and Photocatalysis: Environmental Applications (SPEA) in Strasbourg, France by authors: V. A. de la Peña O’Shea, F. Fresno, J. L. G. Fierro, A. Llobet, H. García, J. J. Vilatela, M. A. García-Aranda, F. Illas, S. Giménez, S. Malato
ORAL PRESENTATION: Boosting photocatalytic CO2 reduction: from inorganic semiconductors to hybrid multifunctional materials
Fernando Fresno presented the talk: "Boosting photocatalytic CO2 reduction: from inorganic semiconductors to hybrid multifunctional materials" in the 9th European meeting on Solar Chemistry and Photocatalysis: Environmental Applications (SPEA) in Strasbourg, France by authors: Patricia Reñones, Fernando Fresno, Laura Collado, Marta Liras, Alba García-Sánchez, Víctor A. de la Peña O’Shea.
New Publication: Nitroxide amide-BODIPY probe behavior in fibroblasts analyzed by advanced fluorescence microscopy
A novel synthesized nitroxide amide-BODIPY prefluorescent probe was used to study cellular redox balance that modulates nitroxide/hydroxylamine ratio in cultured human fibroblasts. FLIM quantitatively differentiated between nitroxide states of the cytoplasm-localized probe imaged by TIRF, monitoring nitroxide depletion by hydrogen peroxide; eluding incorrect interpretation if only fluorescence intensity is considered.
NEW PUBLICATION: Hierarchical TiO2 nanofibres as photocatalyst for CO2 reduction: Influence of morphology and phase composition on catalytic activity
In this research work, the gas phase CO2 photocatalytic reduction using water as electron donor has been performed using hierarchical assemblies of mesoporous TiO2 1-D nanofibres synthesised by a combination of electrospinning and sol–gel methods. In order to compare the effect of the crystallisation step on oxygen vacancies and conductivity, two different annealing conditions have been undertaken: under a high Ar flow (“TiO2 Fibres-A” sample) and under static Ar (“TiO2 Fibres B” sample). Moreover, these materials have been compared with individualised TiO2 nanoparticles prepared by a sol-gel procedure. CO and H2 are detected as major products with all photocatalysts, with lower amounts of CH4 and CH3OH. The TiO2 nanofibres exhibit better results than the sol-gel photocatalyst, behaviour that may be ascribed to an improved nanocrystals connection, which favours a fast charge transport along the grain boundaries, as measured by electrochemical impedance spectroscopy (EIS). The highest CO2 reduction activity is achieved with the TiO2 Fibres B catalyst, which gives rise to ca. 4 and 2.5 times higher H2 and CO production, respectively, than the TiO2 Fibres-A one. This sample is composed of a mixture of anatase and rutile crystalline phases (80:20), leading to a decrease in the electron-hole recombination rate observed by photoluminescence (PL) measurements.
WORKSHOP: Las tecnologías CAC: una oportunidad en la mitigación del cambio climático
Víctor A. de la Peña O´Shea participated in the workshop: “Las tecnologías CAC: una oportunidad en la mitigación del cambio climático” organised by the “Plataforma Tecnológica Española del CO2 (PTECO2)” network in Mérida, Spain.
NEW PUBLICATION: Crystal phase competition by addition of a second metal cation in solid solution metal–organic frameworks
Herein we report a synthetic study focused on the preparation of solid-solution metal–organic frameworks, MOFs, with the use of two kinds of linkers. In particular, we have explored the system composed by zinc, cobalt, 1,2,4-triazole and 4,4′-hexafluoroisopropylidenebisbenzoic acid (H2hfipbb). During this study, four new MOFs have been isolated, denoted TMPF-88 [M3(hfipbb)2(triazole)2(H2O)], TMPF-90 [M2(triazole)3(OCH2CH3)], TMPF-91 [M2(hfipbb)(triazole)2(H2O)] and TMPF-95 [M5(hfipbb)4(triazole)2(H2O)] (TMPF = transition metal polymeric framework, M = Zn, Co, or mixture of them). The study demonstrates that the addition of a second metal element during the MOF synthesis has a major effect in the formation of new phases, even at very high Zn/Co metal ratios. Furthermore, we show that during the MOF formation reaction, there is a competition among different crystal phases, where kinetically favoured phases of various compositions crystallize in short reaction times, precluding the formation of the pure solid-solution phases of other energetically more stable MOFs.
NEW PUBLICATION: Role of the physicochemical properties of hausmannite on the hydrogen production via the MN3O4–Na OH thermochemical cycle
In this work, hausmannite (Mn3O4) is used as the key component of a modified Na–Mn thermochemical cycle for hydrogen production. Although this cycle has a lower theoretical thermodynamic efficiency compared with that using MnO (54% instead of 76%), the reduction of (Mn2O3) to Mn3O4 occurs at temperatures of around 850 °C (about 550 °C lower than for MnO), and these less stringent operation conditions can be advantageous for increasing the durability of materials and reactors. The present study is mainly focused on determining how some relevant physicochemical properties affect the solid reactivity and, consequently, to the efficiency of hydrogen production. For this purpose, Mn3O4 samples with different morphological and textural characteristics were prepared by changing the conditions of the thermal treatment. These materials were characterized by XRD, SEM and temperature programmed reduction (TPR). The obtained results indicate that the surface area of Mn3O4 is the main factor affecting the hydrogen production yield, while the crystalline domain size has minor influence on the efficiency of the process. In order to explore the viability of the thermochemical cycle, the mn3O4 sample that exhibited the highest hydrogen production was submitted firstly to hydrolysis and subsequently to a thermal reduction to recover the initial oxide. This study reveals that, although the removal of Na is not complete in the low temperature stage, reducibility of the solid does not appear to be significantly modified by the presence of these impurities. Overall, these results suggest that the Mn3O4–NaOH can be a viable alternative for the production of solar hydrogen.
New photonic, self-assembled metal-organic frameworks
Researchers from the Instituto de Ciencia de Materiales de Madrid (ICMM) in collaboration with Institut Català de Nanociència i Nanotecnologia (ICN2) have developed highly porous metal-organic particles which spontaneously assemble in tridimensional superstructures. The band gap of this new material can be tuned by changing the size of its particles. This work has been published in Nature Chemistry and can be useful in a number of fields such as catalysis.
New photonic self-assembled metal-organic framework particles
Researchers from the Instituto de Ciencia de Materiales de Madrid (ICMM) in collaboration with Institut Català de Nanociència i Nanotecnologia (ICN2) have developed highly porous metal-organic particles which spontaneously assemble in tridimensional superstructures. The band gap of this new material can be tuned by changing the size of its particles. This work has been published in Nature Chemistry and can be useful in a number of fields such as catalysis.