Emerging Earth-abundant (Fe,Co, Ni,Cu) molecular complexes for solar fuel catalysis

Current micro review focuses on Earth-abundant molecular transition metal photosensitizers and catalysts for dye sensitized photoelectrochemical cells for direct solar energy storage. The possibility of direct conversion of solar energy into fluids (ethanol or methanol) or gases (hydrogen or methane) in a cost efficient way is considered a disruptive and innovative breakthrough for large-scale implementation of solar fuel technologies. At present, it is a fast-growing research area and the most outstanding results are highlighted.     

Semiconductor,molecular and hybrid systems for photoelectrochemical solar fuel production

The paper shortly reviews the basic direct approaches applied in searching for viable solutions to solar fuel production. These are generally distinguished in molecular and semiconductor(non-molecular)systems, however, hybrid strategies, proposed recently, have also been included. The most promising efforts are considered, highlighting key aspects and emerging critical issues. Special attention is paid to aspects such as electrode architecture, device design, and main differences in the scientific vision and challenges to directly produce solar fuels. This overview could be useful to orientate the readers in the wide panorama of research activities concerning water splitting, natural and artificial photosynthesis, and solar fuel production through the identification of common aspects, specialties and potentialities of the many initiatives and approaches that are developing worldwide in this field with the final aim to meet world energy demand.     

Thermochemical solar hydrogen generation

Solar direct, indirect and hybrid thermochemical processes are presented for the generation of hydrogen and compared to alternate solar hydrogen processes. A hybrid solar thermal/electrochemical process combines efficient photovoltaics and concentrated excess sub-bandgap heat into highly efficient elevated temperature solar electrolysis of water and generation of H2 fuel utilizing the thermodynamic temperature induced decrease of E(H2O) with increasing temperature. Theory and experiment is presented for this process using semiconductor bandgap restrictions and combining photodriven charge transfer, with excess sub-bandgap insolation to lower the water potential, and their combination into highly efficient solar generation of H2 is attainable. Fundamental water thermodynamics and solar photosensitizer constraints determine solar energy to hydrogen fuel conversion efficiencies in the 50% range over a wide range of insolation, temperature, pressure and photosensitizer bandgap conditions.     

Efficient solar generation of hydrogen fuel – a fundamental analysis

Solar water splitting can provide clean, renewable sources of hydrogen fuel, although prior models had indicated only low conversion efficiencies would be attainable. A novel model is derived for electrochemical solar water splitting processes by semiconductors, which is the first derivation of band edge restricted thermal enhanced solar water splitting efficiencies. A theoretical basis is developed for solar energy conversion efficiencies in the 50% range as determined with contemporary thermodynamic values. The theory combines photodriven charge transfer, with excess sub-bandgap insolation to lower the water potential, providing a process of highly efficient elevated temperature solar electrolysis of water to hydrogen fuel.     

A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in production of formic acid from CO2

The photocatalyst-enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO(2). The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO(2).     

Inorganic Photocatalysts for Overall Water Splitting

Photocatalytic water splitting using semiconductor photocatalysts has been considered as a “green” process for converting solar energy into hydrogen. The pioneering work on electrochemical photolysis of water at TiO₂ electrode, reported by Fujishima and Honda in 1972, ushered in the area of solar fuel. As the real ultimate solution for solar fuel‐generation, overall water splitting has attracted interest from researchers for some time, and a variety of inorganic photocatalysts have been developed to meet the challenge of this dream reaction. To date, high‐efficiency hydrogen production from pure water without the assistance of sacrificial reagents remains an open challenge. In this Focus Review, we aim to provide a whole picture of overall water splitting and give an outlook for future research.     

Nature-driven photochemistry for catalytic solar hydrogen production: a Photosystem I-transition metal catalyst hybrid

Solar energy conversion of water into the environmentally clean fuel hydrogen offers one of the best long-term solutions for meeting future energy demands. Nature provides highly evolved, finely tuned molecular machinery for solar energy conversion that exquisitely manages photon capture and conversion processes to drive oxygenic water-splitting and carbon fixation. Herein, we use one of Nature's specialized energy-converters, the Photosystem I (PSI) protein, to drive hydrogen production from a synthetic molecular catalyst comprised of inexpensive, earth-abundant materials. PSI and a cobaloxime catalyst self-assemble, and the resultant complex rapidly produces hydrogen in aqueous solution upon exposure to visible light. This work establishes a strategy for enhancing photosynthetic efficiency for solar fuel production by augmenting natural photosynthetic systems with synthetically tunable abiotic catalysts.     

Thermal resistance modeling of oscillating heat pipes filled with acetone by using artificial neural network

Journal of Thermal Analysis and Calorimetry - Oscillating heat pipes (OHPs) are applicable in different energy systems such as solar collectors, desalinations and fuel cells as thermal mediums or...     

Trace water triggers high-efficiency photocatalytic hydrogen peroxide production

Photocatalytic production of hydrogen peroxide(H₂O₂)has attracted much attentions as a promising method for sustainable solar fuel.Here,we demonstrate that trace water can drastically boost highefficiency photocatalytic production of H₂O₂ with a record-high concentration of 113 mmol L^-1 using alkali-assisted C₃N₄ as photocatalyst in water/alcohol mixture solvents.By electron paramagnetic resonance(EPR)measurement,the radical species generated during the photocatalytic process of H₂O₂ are identified.We propose alcohol is used to provide and stabilize-OOH radicals through hydrogen bond,while trace water could trigger photocatalytic production of H₂O₂ via providing and transferring indispensable free protons to completely consume OOH radicals,which breaks the reaction balance of-OOH radical generation from alcohol.Thus-OOH radicals could be supplied by alcohol continuously to serve as a reservoir for high-efficiency production of H₂O₂.These results pave the way towards photocatalytic method on semiconductor catalysts as an outstanding approach for production of hydrogen peroxide.     

From Extended Nanofluidics to an Autonomous Solar‐Light‐Driven Micro Fuel‐Cell Device

Autonomous micro/nano mechanical, chemical, and biomedical sensors require persistent power sources scaled to their size. Realization of autonomous micro‐power sources is a challenging task, as it requires combination of wireless energy supply, conversion, storage, and delivery to the sensor. Herein, we realized a solar‐light‐driven power source that consists of a micro fuel cell (μFC) and a photocatalytic micro fuel generator (μFG) integrated on a single microfluidic chip. The μFG produces hydrogen by photocatalytic water splitting under solar light. The hydrogen fuel is then consumed by the μFC to generate electricity. Importantly, the by‐product water returns back to the photocatalytic μFG via recirculation loop without losses. Both devices rely on novel phenomena in extended‐nano‐fluidic channels that ensure ultra‐fast proton transport. As a proof of concept, we demonstrate that μFG/μFC source achieves remarkable energy density of ca. 17.2 mWh cm⁻² at room temperature.     

钙铝掺杂镧锰钙钛矿高效催化剂用于两步法热化学分解水取得出色产氢表现

太阳能热化学分解水是一种高效生产清洁和可再生氢能源的方法.由于出色的催化活性和太阳能燃料生产能力,钙钛矿型的催化剂在热化学领域引起了强烈关注.我们采用改良的Pechini法合成了一系列钙铝掺杂的镧锰钙钛矿并系统考察了其在两步法热化学分解水中的产氢表现.为了优化热化学催化性能,我们进行了镧锰钙钛矿A,B位上钙和铝的掺杂量(从0.2到0.8)的详细考察.通过调整掺杂比例,得到了一种极其高效的钙钛矿催化剂La0.6Ca0.4Mn0.6Al0.4O3.当两步法热化学分解水在1400和1000℃之间,La0.6Ca0.4Mn0.6Al0.4O3取得了429μmol/g的出色产氢表现,比同等条件下基准催化剂氧化铈产氢结果高出8倍.与此同时,钙铝掺杂镧锰钙钛矿在两步法热化学循环测试中展现出极其稳定的催化活性.因此,这种新颖的钙铝掺杂镧锰钙钛矿具备巨大的潜质用于未来热化学太阳能燃料的实际生产.     

Polymer-fullerene composite solar cells

Fossil fuel alternatives, such as solar energy, are moving to the forefront in a variety of research fields. Polymer-based organic photovoltaic systems hold the promise for a cost-effective, lightweight solar energy conversion platform, which could benefit from simple solution processing of the active layer. The function of such excitonic solar cells is based on photoinduced electron transfer from a donor to an acceptor. Fullerenes have become the ubiquitous acceptors because of their high electron affinity and ability to transport charge effectively. The most effective solar cells have been made from bicontinuous polymer-fullerene composites, or so-called bulk heterojunctions. The best solar cells currently achieve an efficiency of about 5%, thus significant advances in the fundamental understanding of the complex interplay between the active layer morphology and electronic properties are required if this technology is to find viable application.     

过氧化氢生产与利用的新进展

过氧化氢既可用作环境友好的绿色氧化剂,也可用作燃料电池中的太阳能燃料,因而受到越来越多的关注.本文综述了太阳能驱动分子氧氧化水制备过氧化氢及其作为绿色氧化剂和燃料的研究进展.利用太阳能将水的e^-和4e^-氧化与分子氧的e^-还原相结合,使光催化生产过氧化氢成为可能;本文讨论了与e^-和4e^-水氧化选择性及e^-和4e^-氧还原选择性相关的催化反应控制.由于光催化e^-氧化水和e^-还原分子氧的过程都产生过氧化氢,因此该组合的催化效率较高.太阳能光驱动水氧化及分子氧还原生产过氧化氢与过氧化氢催化氧化底物相结合,在该过程中分子氧用作最环保的氧化剂.     

Mimicking Photosynthesis: A Natural Z-Scheme Photocatalyst Constructed from Red Mud Bauxite Waste for Overall Water Splitting

All-solid-state Z-Scheme photocatalysts have attracted significant attention due to their great potential for solar fuel production. However, delicately coupling two individual semiconductors with a charge shuttle by a material strategy remains a challenge. Herein, we demonstrate a new protocol of natural Z-Scheme heterostructures by strategically engineering the component and interfacial structure of red mud bauxite waste. Advanced characterizations elucidated that the hydrogen-induced formation of metallic Fe enabled the effective Z-Scheme electron transfer from γ-Fe₂O₃ to TiO₂, leading to the significantly boosted spatial separation of photo-generated carriers for overall water splitting. To the best of our knowledge, it is the first Z-Scheme heterojunction based on natural minerals for solar fuel production. Thus our work provides a new avenue toward the utilization of natural minerals for advanced catalysis applications.     

面向能源领域的石墨烯研究

化石能源枯竭以及地球环境污染已经成为并且在未来相当长一段时期内都将是人类面临的最严峻的危机之一.因此,寻找清洁的替代能源形式、有效的能量存储方式以及高效的能源利用途径是目前科学研究的热点.自从其高质量样品被制备和研究以来,石墨烯一直吸引着全世界科研工作者的兴趣;它的一系列独特的物理化学性质,为其在能源领域的应用提供了无限前景.本文对石墨烯在能源领域的最新研究进展以及其工业化应用作了简要综述,具体内容包括石墨烯材料在以下领域的应用：能源储存器件类,如超级电容器和锂离子电池;能源转化装置类,如燃料电池和太阳能电池.     

Progress of transition metal chalcogenides as efficient electrocatalysts for energy conversion

The continuous excessive usage of fossil fuels has resulted in its fast depletion, leading to an escalating energy crisis as well as several environmental issues leading to increased research towards sustainable energy conversion. Electrocatalysts play crucial role in the development of numerous novel energy conversion devices, including fuel cells and solar fuel generators. In particular, high-efficiency and cost-effective catalysts are required for large-scale implementation of these new devices. Over the last few years, transition metal chalcogenides have emerged as highly efficient electrocatalysts for several electrochemical devices such as water splitting, carbon dioxide electroreduction, and, solar energy converters. These transition metal chalcogenides exhibit high electrochemical tunability, abundant active sites, and superior electrical conductivity. Hence, they have been actively explored for various electrocatalytic activities. Herein, we have provided comprehensive review of transition-metal chalcogenide electrocatalysts for hydrogen evolution, oxygen evolution, and carbon dioxide reduction and illustrated structure–property correlation that increases their catalytic activity.     

On the pathway of photoexcited electrons: probing photon-to-electron and photon-to-phonon conversions in silicon by ATR-IR

Photoexcitation and charge carrier thermalization inside semiconductor photocatalysts are two important steps in solar fuel production. Here, photoexcitation and charge carrier thermalization in a silicon wafer are for the first time probed by a novel, yet simple and user-friendly Attenuated Total Reflectance Infrared spectroscopy (ATR-IR) system.     

Metal-organic frameworks for energy-related applications

Current micro review describes the recent progress in the energy-related MOF applications. The most outstanding research papers and reviews, which report the application of Metal-Organic Frameworks for gas storage, adsorption heat transformation, solar cells, fuel cells, hydrogen evolution reaction and supercapacitors are highlighted.     

Ternary phase equilibrium studies of the water—ethanol—1,8-cineole system

Ternary liquid—liquid equilibrium data at 25°C were obtained for the water—ethanol—1,8-cineole system, 1,8-cineole being the main component of eucalyptus oil. This study formed one aspect of a project utilizing solar energy stored in plants as liquid fuel components. Experimental results confirmed the absence of phase separation problems in the use of this system as a liquid fuel. The tie-line data for the system were well correlated by the methods of Hand and Othmer—Tobias. The solubility of 1,8-cineole in water was determined over a range of temperatures.     

Quantum Dot Assembly for Light‐Driven Multielectron Redox Reactions,such as Hydrogen Evolution and CO2 Reduction

Light‐driven multielectron redox reactions (e.g., hydrogen (H₂) evolution, CO₂ reduction) have recently appeared at the front of solar‐to‐fuel conversion. In this Minireview, we focus on the recent advances in establishing semiconductor quantum dot (QD) assemblies to enhance the efficiencies of these light‐driven multielectron reduction reactions. Four models of QD assembly are established to promote the sluggish kinetics of multielectron transfer from QDs to cocatalysts, thus leading to an enhanced activity of solar H₂ evolution or CO₂ reduction. We also forecast the potential applications of QD assemblies in other multielectron redox reactions, such as nitrogen (N₂) fixation and oxygen (O₂) evolution from H₂O.