Plasmonic Octahedral Gold Nanoparticles of Maximized Near Electromagnetic Fields for Enhancing Catalytic Hole Transfer in Solar Water Splitting

Due to their localized surface plasmon resonances in visible spectrum, noble metal nanostructures have been considered for improving the photoactivity of wide bandgap semiconductors. Improved photoactivity is attributed to localized surface plasmon relaxations such as direct electron injection and resonant energy transfer. However, the details on the plasmonic solar water splitting through near electromagnetic field enhancement have not been fully understood. Here, the authors report that shape‐controlled gold nanoparticles on wide bandgap semiconductors improve the water‐splitting photoactivity of the semiconductors with over‐bandgap photon energies compared to sub‐bandgap photon energies. It is revealed that hot hole injection into the oxygen evolution reaction potential is the rate‐limiting step in plasmonic solar water splitting. The proposed concept of photooxidation catalysts derived from an ensemble of gold nanoparticles having sharp vertices is applicable to various photocatalytic semiconductors and provides a theoretical framework to explore new efficient plasmonic photoelectrodes.     

Hydrogen generation from photoelectrochemical water splitting based on nanomaterials

Hydrogen is potentially one of the most attractive and environmentally friendly fuels for energy applications. Safe and efficient generation, storage, and utilization of hydrogen present major challenges in its widespread use. Hydrogen generation from water splitting represents a holy grail in energy science and technology, as water is the most abundant hydrogen source on the Earth. Among different methods, hydrogen generation from photoelectrochemical (PEC) water splitting using semiconductors as photoelectrodes is one of the most scalable and cost‐effective approaches. Compared to bulk materials, nanostructured semiconductors offer potential advantages in PEC application due to their large surface area and size‐dependent properties, such as increased absorption coefficient, increased band‐gap energy, and reduced carrier‐scattering rate. This article provides a brief overview of some recent research activities in the area of hydrogen generation from PEC water splitting based on nanostructured semiconductor materials, with a particular emphasis on metal oxides. Both scientific and technical issues are critically analyzed and reviewed.     

Rational design of photoelectrodes for photoelectrochemical water splitting and CO2 reduction

Solar energy has promising potential for building sustainable society. Conversion of solar energy into solar fuels plays a crucial role in overcoming the intermittent nature of the renewable energy source. A photoelectrochemical (PEC) cell that employs semiconductor as photoelectrode to split water into hydrogen or fixing carbon dioxide (CO₂) into hydrocarbon fuels provides great potential to achieve zero-carbon-emission society. A proper design of these semiconductor photoelectrodes thus directly influences the performance of the PEC cell. In this review, we investigate the strategies that have been put towards the design of efficient photoelectrodes for PEC water splitting and CO₂ reduction in recent years and provide some future design directions toward next-generation PEC cells for water splitting and CO₂ reduction.     

Core–Shell Structured Nanocomposites for Photocatalytic Selective Organic Transformations

Core–shell structured nanocomposites, a type of talented functional materials with unique microstructure and properties, have shown great promise as photocatalysts for various applications, including photocatalytic degradation of pollutants, water splitting for hydrogen production, and selective organic transformations. The synthesis and utilization of efficient core–shell nanoarchitectured photocatalysts for selective organic synthesis are at the center of our research efforts and the focus of this minireview. Specifically, semiconductor‐based core–shell nanocomposites, including metal–semiconductor, semiconductor–semiconductor, semiconductor–shell (graphene and SiO₂) as photocatalysts/cocatalysts for selective oxidation of alcohols, reduction of nitro organics and carbon dioxide for synthesis of fine chemicals, and redox‐combined selective synthesis of pipecolinic acid are summarized. It is hoped that this minireview can make a contribution to catalyzing the development of smart core–shell nanostructures in the field of photocatalytic selective organic transformations for solar energy conversion.     

Semiconductor nanowires for photovoltaic and photoelectrochemical energy conversion

Semiconductor nanowires （NW） possess several beneficial properties for efficient conversion of solar energy into electricity and chemical energy. Due to their efficient absorption of light, short distances for minority carriers to travel, high surface-to-volume ratios, and the availability of scalable synthesis methods, they provide a pathway to address the low cost-to-power requirements for widescale adaptation of solar energy conversion technologies. Here we highlight recent progress in our group towards implementation of NW components as photovoltaic and photoelectrochemical energy conversion devices. An emphasis is placed on the unique properties of these one-dimensional （1D） structures, which enable the use of abundant, low-cost materials and improved energy conversion efficiency compared to bulk devices.     

Modulating the properties of monolayer C_2N: A promising metal-free photocatalyst for water splitting

Photocatalytic water splitting has gained increasing attention, since it utilizes renewable resources, such as water and solar energy, to produce hydrogen. Using the first-principles density functional theory, we investigate the properties of the single layer C_2N which was successfully synthesized. We reveal that monolayer C_2N has a substantial direct band gap of 2.45 eV. To regulate its band gap, four different nonmetal elements(B, O, P, and S) on the cation and anion sites are considered. Among them, B-doped N site is the most effective one, with the lowest formation energy and a band gap of 2.01 eV. P-doped N site is the next, with a band gap of 2.08 eV, though its formation energy is higher. The band alignments with respect to the water redox levels show that, for these two dopings, the thermodynamic criterion for the overall water splitting is satisfied. We therefore predict that B-or P-doped C_2N, with an appropriate band gap and an optimal band-edge position, would be a promising photocatalyst for visible-light water splitting.     

Enhanced photosplitting of water using ultrathin cobalt sulfide nanoflakes-sensitized zinc oxide nanorods array

We report synthesis and characterization of ultrathin cobalt sulfide nanoflakes (CoS_x-NFs) sensitized zinc oxide nanorods (Z-NRs) array based thin films and their implementation as photoanodes for photoelectrochemical (PEC) splitting of water. Cobalt sulfide nanoflakes-sensitized zinc oxide nanorods (CoS_x-NFs/Z-NRs) array based photoanodes were grown on fluorine-doped tin oxide substrate by a simple and versatile electrodeposition method. Maximum conversion efficiency of PEC cell was found 0.37% with a photocurrent density of 0.48 mA/cm² at a bias of 0.3 V/SCE in CoS_x-NFs/Z-NRs-15 (loading of CoS_x-NFs on Z-NRs by cyclic voltammetry for 15 cycles) based photoanodes. The photo-activity is 2.7 times larger than that of Z-NRs array-based photoanode. Experimental results reveal that sensitization by CoS_x-NFs causes red shift in the band gap energy of Z-NRs photoanode. Lower band gap energy, suitable band redox potential, and marked absorption in visible light make CoS_x-NFs/Z-NRs-15 thin films a promising material for photoanodes in PEC cells. A detailed analysis using X-ray diffraction (XRD), UV-Visible (UV-Visible) spectroscopy, field emission scanning electron microscope (FE-SEM), energy-dispersive analysis (EDX), electron impedance spectroscopy (EIS), Mott-Schottky (MS) analysis, applied bias photon-to-current conversion efficiency (ABPE), and incident photon to current conversion efficiency (IPCE) measurements has been carried out to substantiate our observations. The excellent performance of CoS_x-NFs/Z-NRs allows the composite photoelectrode to have many potential applications as a photoanode material for H₂ production, nanoflakes-sensitized solar cells, and UV photodetector.     

Photonic crystals for applications in photoelectrochemical processes: Photoelectrochemical solar cells with inverse opal topology

Photonic crystal structures, that present strong light localization effects near photonic band gap frequency regions, can be very useful to maximize chemical processes of phototoactive materials. One example is the use of photonic crystals to improve solar energy harvesting in photoelectrochemical solar cells. Here, we describe the optical monitoring synthesis of macroporous materials, with inverse opal topology, made of transition metal and rare-earth oxide nanoparticles. Through the optical properties we can obtain information concerning both infiltration and over layer growth. Finally, we report on the efficiency improvement of photoelectrochemical cells when titania inverse opal topology is used.     

太阳能光催化制氢的科学机遇和挑战

面对人类对能源的需求持续增长,以及化石能源的日益枯竭和其带来的环境污染问题,太阳能成为主要的可再生清洁能源的来源。讨论了利用太阳能催化生氢或消耗二氧化碳,探索在半导体基光催化剂表面的光催化反应和光化学反应。半导体材料被认为是最有前景的光催化剂,其材料合成是发展先进催化剂的核心。减少电荷重新复合,是提高太阳能转化为化学能的关键,关系到太阳能的转换效率。研究结果发现了提高光催化制氢的关键因素,通过Pt-PdS/CdS催化体系使其量子效率提高到93%,提供了发展高效催化剂体系的方法。     

Review of Sn‐Doped Hematite Nanostructures for Photoelectrochemical Water Splitting

Hematite (α‐Fe₂O₃) nanostructures have been extensively studied as photoanodes for photoelectrochemical (PEC) water splitting. However, the photoactivity of pristine hematite nanostructures is limited by a number of factors, including poor electrical conductiviy and slow oxygen evolution reaction kinetics. Previous studies have shown that using tin (Sn) as an n‐type dopant can substantially enhance the photoactivity of hematite photoanodes by modifying their optical and electrical properties. Here, the recent accomplishments in using Sn‐doped hematite photoanodes for solar water splitting are highlighted.     

纳米材料和技术在可再生能源方面的应用

纳米光子学,产生于纳米技术和光子学的交界处,处理光和物质在纳米尺度的相互作用,可以被用来产生新的效果和发展纳米尺度的器件。世界在迎接未来能源需求方面正面临巨大挑战。纳米光子学为太阳能转换提供了新的进展。在太阳能转换领域,我们正加速开展新的基于纳米光子学让太阳光子在整个光谱范围从紫外到红外有效率地被吸收和转换,并且有效率地转换为电能方面的研究（比如直接或者电化学的转换）。纳米技术也为热电和能量储存方面的研究提供了新的途径,我们正追求把它们和太阳能获取整合在一起从而提供广泛的能源解决方案。     

Hydrogen in amorphous semiconductors

Over the past 5 years, there has been growing interest in a class of amorphous semiconductors deposited in thin-film form in the presence of hydrogen. The interest has derived primarily from certain electronic properties, such as the ability to control the Fermi level by substitutional doping, that make the materials potential candidates for solar photovoltaic energy conversion and thin-film device applications. These same properties have also made the materials attractive “test-beds” for basic research into electronic processes and defect states in amorphous semiconductors.     

Solar cells

Solar cells are based on the photovoltaic effect of converting solar energy into electric energy. The mechanism for solar cells is divided into steps, that is, electron-hole pair generation by absorption of light in semiconductors, separation of electron-hole pairs by built-in potential, electron-hole recombination, collection of charge carriers by metal electrodes, etc. In this article, the principle and the theories of these basic steps are presented. On the basis of these steps, methods to improve the efficiency for solar cells are discussed. The fabrication process and the situation of currently produced solar cells are also presented. Solar cells having no p-n junction, that is, photoelectrochemical solar cells and MIS solar cells, are discussed from the perspective of low-cost solar cells.     

Electrochemical aspects of light-induced heterogeneous reactions on semiconductors

Working mechanisms as photocatalyst of semiconductor particles suspended in solution are reviewed with emphasis on photoelectrochemical aspects. Several techniques useful for determination of electronic energy levels of the photocatalysts and for enhancing apparent photocatalytic activities are described, and their utilities are shown in photodecomposition of water on various kinds of semiconductor particles. Studies on detoxification of inorganic and organic wastes are collected as a promising application field of suspended semiconductor photocatalysts. Finally, significance of the use of quantized semiconductor particles as photocatalysts is discussed.     

Monolayered semiconducting GeAsSe and SnSbTe with ultrahigh hole mobility

High carrier mobility and a direct semiconducting band gap are two key properties of materials for electronic device applications. Using first-principles calculations, we predict two types of two-dimensional semiconductors, ultrathin GeAsSe and SnSbTe nanosheets, with desirable electronic and optical properties. Both GeAsSe and SnSbTe sheets are energetically favorable, with formation energies of −0.19 and −0.09 eV/atom, respectively, and have excellent dynamical and thermal stability, as determined by phonon dispersion calculations and Born–Oppenheimer molecular dynamics simulations. The relatively weak interlayer binding energies suggest that these monolayer sheets can be easily exfoliated from the bulk crystals. Importantly, monolayer GeAsSe and SnSbTe possess direct band gaps (2.56 and 1.96 eV, respectively) and superior hole mobility (~20 000 cm²·V⁻¹·s⁻¹), and both exhibit notable absorption in the visible region. A comparison of the band edge positions with the redox potentials of water reveals that layered GeAsSe and SnSbTe are potential photocatalysts for water splitting. These exceptional properties make layered GeAsSe and SnSbTe promising candidates for use in future high-speed electronic and optoelectronic devices.     

Effect of 10 MeV energy of electron irradiation on Fe<Superscript>2+</Superscript> doped ZnSe nanorods and their modified properties

The Fe²⁺-doped ZnSe nanorods are synthesized using simple potentiostatic mode of electrodeposition on the tin-doped indium oxide (ITO) substrate. To study the effect of electron irradiation, the 10-MeV energy has been applied on 1 % Fe²⁺-doped ZnSe nanorods with different doses such as 10, 20 and 30 kGy. After electron irradiation, structural, morphological, optical, electrochemical and photoelectrochemical properties have been investigated. Due to high energy electron irradiation dose, drastic changes have been observed in the morphological properties; hence, changes have been observed in photoelectrochemical properties also. Due to high-energy, nanorods are destroyed and the photoelectrochemical cell performance (PEC) has been decreased.     

二维GaTe/Bi2Se3异质结：一类有潜力的Z型光解水催化剂

本文基于第一性原理方法,计算了二维GaTe/Bi₂Se₃异质结的电子结构、界面电荷转移、静电势分布、吸收光谱及光催化性质. 计算结果表明异质结是一个小能隙的准直接半导体,能有效捕获太阳光. 由于相对较强的界面內建极化电场和带边轻微弯曲,导致异质结中的光生电子和空穴分别有效分离在GaTe单层和Bi₂Se₃薄片上,可用于析氢和产氧. 这些理论计算结果意味着二维GaTe/Bi₂Se₃异质结是一类有潜力的Z型太阳能全解水催化剂.     

Band structure engineering and defect control of oxides for energy applications

Metal oxides play an essential role in modern optoelectronic devices because they have many unique physical properties such as structure diversity, superb stability in solution, good catalytic activity, and simultaneous high electron conductivity and optical transmission. Therefore, they are widely used in energy-related optoelectronic applications such as photovoltaics and photoelectrochemical(PEC) fuel generation. In this review, we mainly discuss the structure engineering and defect control of oxides for energy applications, especially for transparent conducting oxides(TCOs) and oxide catalysts used for water splitting. We will review our current understanding with an emphasis on the contributions of our previous theoretical modeling, primarily based on density functional theory. In particular, we highlight our previous work:(i) the fundamental principles governing the crystal structures and the electrical and optical behaviors of TCOs;(ii) band structures and defect properties for n-type TCOs;(iii) why p-type TCOs are difficult to achieve;(iv) how to modify the band structure to achieve p-type TCOs or even bipolarly dopable TCOs;(v) the origin of the high-performance of amorphous TCOs; and(vi) band structure engineering of bulk and nano oxides for PEC water splitting. Based on the understanding above, we hope to clarify the key issues and the challenges facing the rational design of novel oxides and propose new and feasible strategies or models to improve the performance of existing oxides or design new oxides that are critical for the development of next-generation energy-related applications.     

卟啉基非金属纳米片用于可见光光催化制氢

本文基于密度泛函理论预测了一种用于可见光范围光催化制氢的新型二维非金属纳米材料,该材料可以由HTAP分子脱氢聚合得到,具有良好的结构稳定性,且带隙为2.12 eV,可以实现可见光区域的光捕获. 材料的带边能级位置恰好包裹水的氧化还原电位,有利于实现全光解水. 电子的迁移率略高于空穴的迁移率,有利于光生载流子的分离. 光生电子可以提供足够的驱动力使得析氢反应自发进行.     

Solar energy conversion with fluorescent collectors

A new principle for solar energy conversion is proposed and evaluated theoretically. Collection and concentration of direct and diffuse radiation is possible by the use of a stack of transparent sheets of material doped with fluorescent dyes. High efficiency of light collection can be achieved by light guiding and special design of collectors. The optical path length in a triangular collector is computed. In combination with solar cells this type of collector offers the advantage of separating the various fractions of light and converting them with solar cells with different bandgaps. Theoretical conversion efficiency under optimum conditions is 32% for a system with four semiconductors. Thermal energy conversion offers several advantages over conventional collectors: High temperature and efficiency even under weak illumination, separation of heat transport and radiation collection, low thermal mass. Thermal efficiency is computed to be between 42% and 60%. Very attractive appear hybrid systems for generation of thermal and electric energy. An estimate of the economics of electricity generation shows that due to the concentration costs can be much lower than possible today. With the use of only silicon cells the breakeven point of $0.5/W is almost reached. Practical difficulties to be solved are: Synthesis of dyes with stringent requirements, identification of plastic materials with high transparency and development of solar cells with higher bandgaps.