铁基多相助催化剂光电化学水氧化研究进展

The use of fossil fuels has caused serious environmental problems such as air pollution and the greenhouse effect. Moreover, because fossil fuels are a non-renewable energy source, they cannot meet the continuously increasing demand for energy. Therefore, the development of clean and renewable energy sources is necessitated. Hydrogen energy is a clean, non-polluting renewable energy source that can ease the energy pressure of the whole society. The sunlight received by the Earth is 1.7× 10¹⁴ J in 1 s, which far exceeds the total energy consumption of humans in one year. Therefore, conversion of solar energy to valuable hydrogen energy is of significance for reducing the dependence on fossil fuels. Since Fujishima and Honda first reported on TiO₂ in 1972, it has been discovered that semiconductors can generate clean, pollution-free hydrogen through water splitting driven by electricity or light. Hydrogen generated through this approach can not only replace fossil fuels but also provide environmentally friendly renewable hydrogen energy, which has attracted considerable attention. Photoelectrochemical (PEC) water splitting can use solar energy to produce clean, sustainable hydrogen energy. Because the oxygen evolution reaction (OER) over a photoanode is sluggish, the overall energy conversion efficiency is considerably low, limiting the practical application of PEC water splitting. A cocatalyst is, thus, necessary to improve PEC water splitting performance. So far, the synthesis of first-row transition-metal-based (e.g., Fe, Co, Ni, and Mn) cocatalysts has been intensively studied. Iron is earth-abundant and less toxic than other transition metals, making it a good cocatalyst. In addition, iron-based compounds exhibit the properties of a semiconductor/metal and have unique electronic structures, which can improve electrical conductivity and water adsorption. Various iron-based catalysts with high activity have been designed to improve the efficiency of PEC water oxidation. This article briefly summarizes the research progress related to the structure, synthesis, and application of iron oxyhydroxides, iron-based layered double hydroxides, and iron-based perovskites and discusses the evaluation of the performance of these cocatalysts toward photoelectrochemical water oxidation.      

Integrated Photoelectrochemical Solar Energy Conversion and Organic Redox Flow Battery Devices

Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost‐effective hybrid energy conversion and storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10‐anthraquinone‐2,7‐disulfonic acid (AQDS)/1,2‐benzoquinone‐3,5‐disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L^?1 and a solar‐to‐output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency.     

Emerging materials for plasmon-assisted photoelectrochemical water splitting

Energy production and environmental pollution are the two major problems the world is facing today. The depletion of fossil fuels and the emission of harmful gases into the atmosphere leads to the research on clean and renewable energy sources. In this context, hydrogen is considered an ideal fuel to meet global energy needs. Presently, hydrogen is produced from fossil fuels. However, the most desirable way is from clean and renewable energy sources, like water and sunlight. Sunlight is an abundant energy source for energy harvesting and utilization. Recent studies reveal that photoelectrochemical (PEC) water splitting has promise for solar to hydrogen (STH) conversion over the widely tested photocatalytic approach since hydrogen and oxygen gases can be quantified easily in PEC. For designing light-absorbing materials, semiconductors are the primary choice that undergoes excitation upon solar light irradiation to produce excitons (electron-hole pairs) to drive the electrolysis. Visible light active semiconductors are attractive to achieve high solar to chemical fuel conversion. However, pure semiconductor materials are far from practical applications because of charge carrier recombination, poor light-harvesting, and electrode degradation. Various heteronanostructures by the integration of metal plasmons overcome these issues. The incorporation of metal plasmons gained significance for improving the PEC water splitting performance. This review summarizes the possible main mechanisms such as plasmon-induced resonance energy transfer (PIRET), hot electron injection (HEI), and light scatting/trapping. It also deliberates the rational design of plasmonic structures for PEC water splitting. Furthermore, this review highlights the advantages of plasmonic metal-supported photoelectrodes for PEC water splitting.     

Conversion of Solar Energy to Fuels by Inorganic Heterogeneous Systems

Over the last several years,the need to find clean and renewable energy sources has increased rapidly because current fossil fuels will not only eventually be depleted,but their continuous combustion leads to a dramatic increase in the carbon dioxide amount in atmosphere.Utilisation of the Sun’s radiation can provide a solution to both problems.Hydrogen fuel can be generated by using solar energy to split water,and liquid fuels can be produced via direct CO2 photoreduction.This would create an essentially free carbon or at least carbon neutral energy cycle.In this tutorial review,the current progress in fuels’ generation directly driven by solar energy is summarised.Fundamental mechanisms are discussed with suggestions for future research.     

Water‐Splitting Catalysis and Solar Fuel Devices: Artificial Leaves on the Move

The development of new energy materials that can be utilized to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks in science today. Solar‐powered catalytic water‐splitting processes can be exploited as a source of electrons and protons to make clean renewable fuels, such as hydrogen, and in the sequestration of CO₂ and its conversion into low‐carbon energy carriers. Recently, there have been tremendous efforts to build up a stand‐alone solar‐to‐fuel conversion device, the “artificial leaf”, using light and water as raw materials. An overview of the recent progress in electrochemical and photo‐electrocatalytic water splitting devices is presented, using both molecular water oxidation complexes (WOCs) and nano‐structured assemblies to develop an artificial photosynthetic system.     

Revolutionary Times

This perspective article presents the author's views on the current revolutionary time in society and science, driven by the actions to mitigate climate change and the targets in the decrease of CO₂ emissions. Due to the short time scale needed to implement large-scale renewable electricity schemes, new technologies on how to store huge amounts of electric energy have to be implemented. One possibility is the production of hydrogen from water using renewable electricity, which also open up new avenues to perform ammonia and methanol syntheses. The future application of photocatalysis using direct sunlight for the production of solar fuels is also discussed, commenting on which are the most promising photocatalytic reactions that are close to become tested on pilot scales.     

Decoupled Artificial Photosynthesis

Natural photosynthesis (NP) generates oxygen and carbohydrates from water and CO₂ utilizing solar energy to nourish lives and balance CO₂ levels. Following nature, artificial photosynthesis (AP), typically, overall water or CO₂ splitting, produces fuels and chemicals from renewable energy. However, hydrogen evolution or CO₂ reduction is inherently coupled with kinetically sluggish water oxidation, lowering efficiencies and raising safety concerns. Decoupled systems have thus emerged. In this review, we elaborate how decoupled artificial photosynthesis (DAP) evolves from NP and AP and unveil their distinct photoelectrochemical mechanisms in energy capture, transduction and conversion. Advances of AP and DAP are summarized in terms of photochemical (PC), photoelectrochemical (PEC), and photovoltaic-electrochemical (PV-EC) catalysis based on material and device design. The energy transduction process of DAP is emphasized. Challenges and perspectives on future researches are also presented.     

太阳能光催化制氢研究进展

随着人类社会的快速发展和传统能源的急剧消耗,能源紧缺和环境污染已经成为制约人类社会可持续发展的重要因素,构建清洁的环境友好的可再生新能源体系是当前各国高度关注的焦点和重大战略.在众多绿色环保、可持续新能源选项中,半导体光催化制氢因其可利用清洁可再生的太阳能制取高效清洁氢能,有望完全解决能源紧缺和环境污染问题,成为最有应用前景的技术之一. 本文通过概述半导体光催化制氢原理、半导体光电化学及光电稳定性、半导体光催化制氢效率,重点介绍半导体光催化剂、光生电荷分离及光催化制氢体系等方面若干新进展,并对太阳能光催化制氢技术的发展加以评述和展望.     

宽光谱太阳能电池

太阳能电池的光谱响应特性和光电转换效率与光伏材料的微观能带结构及其宏观组装方式密切相关。无论使用哪种光伏材料,普通单结或单层太阳能电池都只能对部分波段的太阳光进行有效利用。宽光谱研究的目标是要使太阳能电池更好地利用太阳光谱所覆盖的全部波段范围的能量,从而提高太阳能电池光电转换效率。本文从化学角度综述了实现宽光谱太阳能电池的基本方法和当前的研究进展,其中包括叠层太阳能电池、中间带太阳能电池、量子点太阳能电池、热光伏太阳能电池、上转换和下转换、分子基柔性太阳能电池等方法。     

Recent Progress on Semi-transparent Perovskite Solar Cell for Building-integrated Photovoltaics

The electricity consumption of buildings is tremendous; moreover, a huge amount of electricity is lost during distribution. Taking away this consumption can significantly reduce energy demand and greenhouse effect gas emission. One of the low-cost and renewable solutions to this issue is to install photovoltaic panels on the buildings themselves, namely, building-integrated photovoltaics(BIPVs). Using this technology, power generation roofs, windows, and facades can harvest solar radiation and convert to electricity for building power consumption. Semi-transparent perovskite solar cells(ST-PSCs) have attracted tremendous attention for the power generation windows, due to the excellent photoelectric properties, versatile fabrication methods, bandgap tunability, and flexibility. Here, an overview is provided on the recent progress of ST-PSCs for BIPV, which mainly focuses on the control of perovskite morphology, optical engineering for an efficient and semi-transparent ST-PSC. We also summarize recent development on various transparent electrodes and present prospects and challenges for the commercialization of ST-PSCs.     

Stipulating Low Production Cost Solar Cells All Set to Retail…!

Today's solar cells are exceptionally in demand whilst excess exploitation of natural fossil fuels. In this context, the first and second generation solar cells commercially available in market for more than decades however limitations in production cost and large–scale applications insist to generate inexpensive materials for fabrication. Thereby, organic materials based solar cells explored and emerging as third generation solar cells which possess flexibility, low cost and large‐scale applications. For example, organic photovoltaics, dye sensitized solar cells and perovskite (organic‐inorganic) solar cells (PSCs) are considered third generation solar cells wherein PSCs reached the record power conversion efficiency (PCE ～23 %) and durability assists great advantages for commercialization in near future. Moreover, we reported various global renowned companies involved producing the modules and materials for three generation solar cells, hence, majority of companies considered commercialization of perovskite based solar cells assist low cost photovoltaics to meet the current energy necessities and environmental safety.     

Biological Components and Bioelectronic Interfaces of Water Splitting Photoelectrodes for Solar Hydrogen Production

Artificial photosynthesis (AP) is inspired by photosynthesis in nature. In AP, solar hydrogen can be produced by water splitting in photoelectrochemical cells (PEC). The necessary photoelectrodes are inorganic semiconductors. Light‐harvesting proteins and biocatalysts can be coupled with these photoelectrodes and thus form bioelectronic interfaces. We expand this concept toward PEC devices with vital bio‐organic components and interfaces, and their integration into the built environment.     

Understanding Surface Recombination Processes Using Intensity-Modulated Photovoltage Spectroscopy on Hematite Photoanodes for Solar Water Splitting

Converting solar energy into hydrogen through photoelectrochemical (PEC) water splitting offers a promising route towards a fully renewable energy economy. A fundamental understanding of photogenerated charge recombination processes in semiconducting photoelectrodes is a key consideration in optimizing solar water splitting cells and intensity-modulated photovoltage spectroscopy (IMVS) has recently emerged as a promising technique for gaining new insight. However, the interpretation of IMVS data under various conditions (that is, when photoelectrodes are in sacrificial electrolytes or employ catalytic overlayers) is not complete. Using IMVS data we present herein an analysis of charge recombination processes under open circuit conditions on a model photoanode system: nanostructured hematite. Employing two sacrificial oxidation conditions compared to standard water oxidation conditions, our IMVS results establish a direct correlation between surface recombination processes and the low frequency IMVS response. We found that surface intermediate states for water oxidation under open circuit condition exhibit a lifetime of 229 ms under standard illumination conditions. Applying a nickel iron oxide overlayer also gives insight into surface passivation effects through IMVS analysis of photoanode system.     

《光电化学及新型太阳能电池》专辑序言

众所周知,能源与环境是当今人类面临的最大难题和挑战,随着世界能源需求的急剧攀升,传统化石资源的不断耗竭,全球温室效应和环境污染的压力日趋严重,发展各种可再生绿色能源成为当今世界最主要的共性问题和研究热点. 太阳能光电转化技术被认为是一种最有希望真正解决未来社会可再生能源和洁净环境问题的先进技术. 太阳可为人类提供取之不尽、用之不竭的巨大能源宝库,每年照射到地球的太阳能量高达174000TW,换言之,只要能以10%效率转化0.1%到达地球表面的太阳能,即可满足全球的能源需求. 当前国际上最热点研究的新型太阳能电池包括染料敏化太阳能电池、有机太阳能电池、量子点太阳能电池及钙钛矿太阳能电池等,这些新型太阳能电池的研究近年来取得了长足的进步,世界上每年发表相关论文超过10000篇,其中中国学者在太阳能光电化学理论、光电转化器件设计、电极材料、有机半导体光伏材料、电解质系统、有机及钙钛矿太阳能电池电极界面修饰层材料等方面开展了大量卓有特色的工作,为推进各种新型太阳能电池的进步和应用做出不菲的贡献. 光电化学是一门研究光与电化学相互作用的交叉学科,是太阳能高效利用中光-电转化和光能-化学能转化的核心理论基础. 自上世纪70年代以来,光电化学理论得到不断发展和完善,为当今蓬勃发展的各种新型太阳能电池和光催化制氢等提供了强有力的理论指导. 然而,随着纳米科技、材料科学及半导体物理等现代科技的飞速发展和多学科深入研究,诸多新型太阳能体系研究的新现象和复杂性仍未能得到圆满解析. 仍亟需进一步从微观水平认识太阳能电化学电池及光电催化的反应本质,发展原位表征和超快时间分辨技术研究光生电子的传输、复合及界面反应等规律及定量关系,为人们设计高光电转化效率的电化学太阳能电池、推进商品化应用提供理论指导. 本专辑围绕光电化学及新型太阳能电池专题,收录了在相关研究领域具有丰富积累和影响的团队所撰写的9篇相关研究进展的综述文章和研究论文,部分反映了我国在新型太阳能电池结构设计、合成方法和性能研究方面的研究进展.希望借助该专刊的出版,能使广大读者更深入地了解我国在新型太阳能电池领域的研究现状、研究趋势和存在的问题及挑战,推动我国光电化学及新型太阳能电池研究的进一步发展. 在此,对本专辑的所有作者、审稿人及编辑部工作人员的卓有成效的工作和付出表示衷心的感谢！     

Use of Solar Power for Heat Generation for Household Application

The requirement of getting continuous electricity at low cost is essential but challenging. Especially in the undeveloped countries there is no sufficient electricity for the people to do their daily regular works. In order to overcome this problem different renewable energy sources are sought and being explored. One of the approaches is to have a cooking system that is energized from the solar power, not directly using a solar cooker but by storing the energy in the form of heat that can be utilized as per requirement. This paper reports the design and fabrication of an alternative system to generate heat using solar radiation. This chulha is helpful in effective heating with the help of solar radiations at lower costs. A cooking technology is presented consisting of a solar panel directly connected to an electric heater inside of a well-insulated chamber. An insulated container with fixed amount of oil is heated up. The heat is found to be retained in the chamber even after sun set which is sufficient for heating water for making tea. The possible causes of temperature drop and possible remedy has been pointed out and discussed in this paper.     

电化学氢压缩和纯化与竞争技术的对比:Ⅰ.优缺点

毫无疑问,氢将在我们未来的能量组合中发挥重要作用,因为它可以储存可再生电(电-氢)并在燃料电池中可逆地转化为电能,更不用说它在(石油)化学工业中的广泛应用了.然而,在这些应用中需要纯氢,而如今的制氢仍主要基于化石燃料,因而不能被视为纯氢.因此,大规模的氢气净化是必须的.此外,氢是最轻的气体,它的体积能量含量远远低于它的竞争燃料,除非它在高压下被压缩(通常70MPa),使压缩不可避免.本文将详细说明目前可用于氢气净化和压缩的方法.这将表明在现有的技术中,也可以实现氢气净化的电化学氢压缩机(EHC)与目前工业规模上使用的经典技术相比具有许多优势.EHC有其热力学和操作上的优点,但也易于使用.然而,只有达到足够的性能, EHCs的部署才是可行的,这意味着他们的基础材料应遵守一些规范.本文将详述这些规范.     

Enhanced Conversion Efficiency Enabled by Species Migration in Direct Solar Energy Storage

Solar energy can be stored via either an indirect route in which electricity is involved as an intermediate step, or a direct route that utilizes photogenerated charge carriers for direct solar energy conversion. In this study, we investigate the fundamental difference between the direct and indirect routes in solar energy conversion using a new photoelectrochemical energy storage cell (PESC) as a model device. This PESC centers on a liquid junction that utilizes CH₃NH₃PbI₃ perovskite to drive photoelectrochemical reactions of Benzoquinone (BQ) and Ferrocene (Fc) redox species. The experimental studies show that the equilibrium redox potentials are 0.1 V and −0.78 V (vs Ag/AgNO₃) for Fc⁺/Fc and BQ/BQ^.−, respectively, which would produce a theoretical open-circuit voltage of 0.88 V for the storage device. The physics-based computational analysis shows a relatively flat reaction rate distribution in the electrode for the indirect route; however, in the direct route the photoelectrochemical reaction rate is critically affected by electron concentration due to strong light absorption of the perovskite material, which has been shown to vary by at least 10-fold in the transverse direction across the photoelectrode. The drastic variation of reaction rate in the photoelectrode creates an electric field that is 7.5 times stronger than the bulk electrolyte, which causes the photo-converted reaction product (i. e., BQ^.−) to drift away from the photoelectrode thereby creating a constant reaction driving force. As a result, it has been shown that the intrinsic solar to chemical conversion (ISTC) efficiency improves by ∼40 % for the direct route compared to the indirect route at 0.05 mA/cm².     

Perovskite Solar Cells: From the Atomic Level to Film Quality and Device Performance

Organic–inorganic perovskites have made tremendous progress in recent years due to exceptional material properties such as high panchromatic absorption, charge carrier diffusion lengths, and a sharp optical band edge. The combination of high‐quality semiconductor performance with low‐cost deposition techniques seems to be a match made in heaven, creating great excitement far beyond academic ivory towers. This is particularly true for perovskite solar cells (PSCs) that have shown unprecedented gains in efficiency and stability over a time span of just five years. Now there are serious efforts for commercialization with the hope that PSCs can make a major impact in generating inexpensive, sustainable solar electricity. In this Review, we will focus on perovskite material properties as well as on devices from the atomic to the thin film level to highlight the remaining challenges and to anticipate the future developments of PSCs.     

Nanocatalysts for Solar Water Splitting and a Perspective on Hydrogen Economy

In this review article, nanocatalysts for solar hydrogen production are the focus of discussion as they can contribute to the development of sustainable hydrogen production in order to meet future energy demands. Achieving this task is subject of scientific aspirations in the field of photo‐ and photoelectrocatalysis for solar water splitting where systems of single catalysts or tandem configurations are being investigated. In search of a suitable catalyst, a number of crucial parameters are laid out which need to be considered for material design, in particular for nanostructured materials that provide exceptional physical and chemical properties in comparison to their bulk counterparts. Apart from synthetic approaches for nanocatalysts, key parameters and properties of nanostructured photocatalysts such as light absorption, charge carrier generation, charge transport, separation and recombination, and other events that affect nanoscale catalysts are discussed. To provide a deeper understanding of these key parameters and properties, their contribution towards existing catalyst systems is evaluated for photo‐ and photoelectrocatalytic solar hydrogen evolution. Finally, an insight into hydrogen production processes is given, stressing the current development of sustainable hydrogen sources and presenting a perspective towards a hydrogen‐based economy.     

Solar energy conversion from water photolysis by biological and chemical systems

The production of chemicals and fuels, or energy-rich compounds, from water by sunlight is described as a particularly attractive means for the conversion of solar energy to a valuable renewable resource. The redox properties of photoexcited molecules and the operating mechanism of light-driven systems are first considered. The mechanism of water oxidation carried out by higher plants and green algae-which is actually one of the most important biochemical reactions—as well as that of artificial photosystems, up-to-now designed trying to simulate the natural process with higher efficiency and simplicity, are likewise discussed. A number of biological and chemical light-driven systems are presented as practical ways to solar energy conversion.