Recent Advances in Visible-Light-Driven Photoelectrochemical Water Splitting: Catalyst Nanostructures and Reaction Systems

Photoelectrochemical(PEC) water splitting using solar energy has attracted great attention for generation of renewable hydrogen with less carbon footprint, while there are enormous challenges that still remain for improving solar energy water splitting efficiency, due to limited light harvesting, energy loss associated to fast recombination of photogenerated charge carriers, as well as electrode degradation. This overview focuses on the recent development about catalyst nanomaterials and nanostructures in different PEC water splitting systems. As photoanode, Au nanoparticle-decorated TiO_2 nanowire electrodes exhibited enhanced photoactivity in both the UV and the visible regions due to surface plasmon resonance of Au and showed the largest photocurrent generation of up to 710 nm. Pt/Cd S/CGSe electrodes were developed as photocathode. With the role of p–n heterojunction, the photoelectrode showed high stability and evolved hydrogen continuously for more than 10 days. Further, in the Z-scheme system(Bi_2S_3/TNA as photoanode and Pt/Si PVC as photocathode at the same time), a self-bias(open-circuit voltage Voc= 0.766 V) was formed between two photoelectrodes, which could facilitate photogenerated charge transfers and enhance the photoelectrochemical performance, and which might provide new hints for PEC water splitting. Meanwhile, the existing problems and prospective solutions have also been reviewed.

Insights on advanced substrates for controllable fabrication of photoanodes toward efficient and stable photoelectrochemical water splitting

Conversion of solar energy into H_(2) by photoelectrochemical(PEC)water splitting is recognized as an ideal way to address the growing energy crisis and environmental issues.In a typical PEC cell,the construction of photoanodes is crucial to guarantee the high efficiency and stability of PEC reactions,which fundamentally rely on rationally designed semiconductors(as the active materials)and substrates(as the current collectors).In this review work,we start with a brief introduction of the roles of substrates in the PEC process.Then,we provide a systematic overview of representative strategies for the controlled fabrication of photoanodes on rationally designed substrates,including conductive glass,metal,sapphire,silicon,silicon carbide,and flexible substrates.Finally,some prospects concerning the challenges and research directions in this area are proposed.

基于需求响应的电热综合能源市场MPEC优化

为促进电热综合能源市场多能流协同消纳,减少负荷不平衡所带来用能波动的问题,基于价格弹性矩阵建立电、热需求响应模型,以能量枢纽为利益主体,利用均衡约束数学规划模型,制定综合能源市场竞标策略。实现电、热网运营商运行成本最小的同时,使能量枢纽运营主体获得最大收益,并且有效降低系统总耗能。结果表明,系统在综合需求响应机制的作用下削峰填谷、平衡系统用能,以能量枢纽获益降低160.44元为代价,换取减少能耗2.3 MW,且冬夏两季能量枢纽收益和系统整体能耗百分比变化较小,分别为3.42%和0.604%。

Rate Law for Photoelectrochemical Water Splitting Over CuO

Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.

求解一类MPEC问题的一种UV-分解方法

给出了求解具有线性互补约束的MPEC问题的一种UV-分解方法.首先将MPEC问题化为非线性规划问题,给出一种相应的罚函数的次微分结构及其UV-分解的结果,根据所得到的结果构造一个具有超线性收敛速度的概念型算法.

Electrodeposition of Cu_2O/g-C_3N_4 heterojunction film on an FTO substrate for enhancing visible light photoelectrochemical water splitting

An immobilized Cu2O/g-C3N4 heterojunction film was successfully made on an FTO substrate by electrophoretic deposition of g-C3N4 on a Cu2O thin film.The photoelectrochemical（PEC） performance for water splitting by the Cu2O/g-C3N4 film was better than pure g-C3N4 and pure Cu2O film.Under-0.4 V external bias and visible light irradiation,the photocurrent density and PEC hydrogen evolution efficiency of the optimized Cu2O/g-C3N4 film was-1.38 mA/cm^2 and 0.48 mL h^-1 cm^-2,respectively.The enhanced PEC performance of Cu2O/g-C3N4 was attributed to the synergistic effect of light coupling and a matching energy band structure between g-C3N4 and Cu2O as well as the external bias.

松弛MPEC和MIQP的启发–校正两阶段动态无功优化算法

为快速求解计及离散调节设备动作次数约束和电网安全约束的多时段动态无功优化问题,建立以有功网损最小为目标函数的混合整数非线性规划模型,并提出一种启发搜索加变量校正的两阶段求解方法:启发搜索首先将离散变量松弛为连续变量,形成一个带平衡约束的的优化模型,进而得到各个时段的连续优化结果,然后建立以方差最小化为目标并严格满足原模型中离散调节设备动作次数约束的整数二次规划模型,得到最优动作次数和离散归整结果;变量校正是固定启发搜索得到的离散变量优化结果,重新校正连续变量的优化量。通过IEEE 14测试系统详细讨论了无功调节设备的步长和动作次数对优化结果的影响;此外,IEEE 30、57、118节点测试系统的优化结果表明,所提方法能够快速得到优化结果,实现并行求解,且其精度可满足实际工程需要。

一类MPEC问题的SQP算法

本文研究带线性互补约束规划问题的 SQP算法 .该算法不要求精确计算初值 ,是针对初值非精确计算情形的新算法 ,证明了该算法的收敛性 .

Photoelectrochemical degradation of acetaminophen and valacyclovir using nanoporous titanium dioxide

Electrochemically treated nanoporous TiO2 was employed as a novel electrode to assist in the pho- toelectrochemical degradation of acetaminophen and valacyclovir. The prepared electrode was characterized by scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS）. Cyclic voltammetry （CV）, Mott-Schottky plots, ultraviolet-visible light （UV-vis） absorbance spec- troscopy, and a total organic carbon （TOC） analyzer were employed to investigate the photoelec- trochemical degradation of acetaminophen and valacyclovir. The results indicated no obvious re- moval of acetaminophen and valacyclovir over 3 h when separate photochemical degradation and electrochemical oxidation were employed. In contrast, acetaminophen and valacyclovir were rapid- ly eliminated via photoelectrochemical degradation. In addition, electrochemically treated nanopo~ rous TiO2 electrodes significantly enhanced the efficacy of the photoelectrochemical degradation of acetaminophen and valacyclovir, by 86.96% and 53.12%, respectively, when compared with un- treated nanoporous TiO2 electrodes. This enhanced performance may have been attributed to the formation of Ti3~, Ti2~, and oxygen vacancies, as well as an improvement in conductivity during the electrochemical reduction process. The effect of temperature was further investigated, where the activation energy of the photoelectrochemical degradation of acetaminophen and valacyclovir was determined to be 9.62 and 18.42 kJ/mol, respectively.

MPEC问题的精确罚函数法收敛性

应用精确罚函数方法,将MPEC问题转化为目标函数含有罚项的一般约束优化问题。当罚因子足够大时,该约束优化问题的极小点收敛于原问题的极小点。

MPEC问题的带任意初值的一类算法

研究了求解带线性互补约束优化问题的一种新算法 ,其中新算法 w0可任意选取 .算例表明 。

Enhanced Performance of a Monolayer MoS_2/WSe_2 Heterojunction as a Photoelectrochemical Cathode

Transition-metal dichalcogenide(TMD) semiconductors have attracted interest as photoelectrochemical(PEC) electrodes due to their novel band-gap structures,optoelectronic properties, and photocatalytic activities.However, the photo-harvesting efficiency still requires improvement. In this study, A TMD stacked heterojunction structure was adopted to further enhance the performance of the PEC cathode. A P-type WSe_2 and an N-type Mo S_2 monolayer were stacked layer-by-layer to build a ultrathin vertical heterojunction using a micro-fabrication method.In situ measurement was employed to characterize the intrinsic PEC performance on a single-sheet heterostructure.Benefitting from its built-in electric field and type II band alignment, the MoS_2/WSe_2 bilayer heterojunction exhibited exceptional photocatalytic activity and a high incident photo-to-current conversion efficiency(IPCE). Comparing with the monolayer WSe_2 cathode, the PEC current and the IPCE of the bilayer heterojunction increased by a factor of 5.6 and enhanced 50%, respectively. The intriguing performance renders the MoS_2/WSe_2 heterojunction attractive for application in high-performance PEC water splitting.

A review on photoelectrochemical cathodic protection semiconductor thin films for metals

Photoelectrochemical(PEC) cathodic protection is considered as an environment friendly method for metals anticorrosion. In this technology, a n-type semiconductor photoanode provides the photogenerated electrons for metal to achieve cathodic protection. Comparing with traditional PEC photoanode for water splitting, it requires the photoanode providing a suitable cathodic potential for the metal, instead of pursuit ultimate photon to electric conversion efficiency, thus it is a more possible PEC technology for engineering application. To date, great efforts have been devoted to developing novel n-type semiconductors and advanced modification method to improve the performance on PEC cathodic protection metals. Herein, recent progresses in this field are summarized. We highlight the fabrication process of PEC cathodic protection thin film, various nanostructure controlling, doping, compositing methods and their operation mechanism. Finally, the current challenges and future potential works on improving the PEC cathodic protection performance are discussed.

ABS算法在求解MPEC问题中的应用

应用ABS—隐式LU算法,简化MPEC问题的约束条件,将简化后的MPEC问题转化为目标函数带有罚函数子项的非线性无约束优化问题,给出收敛性定理,证明当罚因子足够大时,此非线性无约束问题的极小点就是简化后的MPEC问题的极小点,将此极小点代入本文中给出的一个转换公式可得原MPEC问题的极小点,文末给出一算例。

Efficient Photoelectrochemical Water Splitting by g-C_3N_4/TiO_2 Nanotube Array Heterostructures

Well-ordered TiO_2 nanotube arrays(TNTAs)decorated with graphitic carbon nitride(g-C_3N_4) were fabricated by anodic oxidization and calcination process.First, TNTAs were prepared via the anodic oxidation of Ti foil in glycerol solution containing fluorinion and 20%deionized water. Subsequently, g-C_3N_4 film was hydrothermally grown on TNTAs via the hydrogen-bonded cyanuric acid melamine supramolecular complex. The results showed that g-C_3N_4 was successfully decorated on the TNTAs and the g-C_3N_4/TNTAs served as an efficient and stable photoanode for photoelectrochemical water splitting. The facile deposition method enables the fabrication of efficient and low-cost photoanodes for renewable energy applications.

Photoelectrochemical study of MoO_3 assorted morphology films formed by thermal evaporation

Molybdenum oxide nanostructured thin films were grown on fluorine doped tin oxide（FTO）, indium doped tin oxide（ITO） and ordinary glass substrates by thermal evaporation process without vacuum and catalysts using molybdenum trioxide（MoO） powder as a source material and oxygen as a carrier gas.Various morphologies including nanobelts, disks and hexagonal rod-like nanostructures were obtained by changing the source and substrate temperatures during the growth of MoOthin films. Structural parameters, morphology, composition and surface features of the films were characterized by XRD, SEM, EDAX,XPS, AFM and Raman spectroscopy. The films were orthorhombic in structure with preferred orientation along（0 1 0） plane. Morphology analysis reveals randomly aligned nanobelts with 40 nm in thickness and a width of 800 nm and 3–12 mm in length. The disks have 1.5 μm diameters, 1 μm thickness and hexagonal rod-like nanostructures with a length, breath and width of 2 μm, 1 μm and 100 nm are formed. The samples were investigated under dark and photocurrent conditions in HSOaqueous solution as a function of applied potential. The photocurrent density of samples prepared on ITO and FTO substrate samples were compared and the results are discussed.

A Facile Self-assembly Synthesis of Hexagonal ZnO Nanosheet Films and Their Photoelectrochemical Properties

Here, large-scale and uniform hexagonal zinc oxide(ZnO) nanosheet films were deposited onto indium tin oxide(ITO)-coated transparent conducting glass substrates via a facile galvanic displacement deposition process. Compared with other commonly used solution methods, this process avoids high temperature and electric power as well as supporting agents to make it simple and cost-effective. The as-fabricated ZnO nanosheet films have uniform hexagonal wurtzite structure. The photoelectrochemical(PEC) cell based on ZnO nanosheet film/ITO photoelectrode was also fabricated and its performance was improved by optimizing the solution concentration. A higher photocurrent density of*500 l A cm^(-2)under AM 1.5 G simulated illumination of 100 m W cm^(-2)with zero bias potential(vs. Ag/AgCl electrode) was obtained, which may ascribe to the increased surface-to-volume ratio of disordered Zn O nanosheet arrays. Our developed method may be used to deposit other oxide semiconductors, and the Zn O nanosheet film/ITO PEC cell can be used to design low-cost optoelectronic and photoelectrochemical devices.

Highly Enhanced Visible-Light-Driven Photoelectrochemical Performance of ZnO-Modified In_2S_3 Nanosheet Arrays by Atomic Layer Deposition

Photoanodes based on In_2S_3/ZnO heterojunction nanosheet arrays(NSAs) have been fabricated by atomic layer deposition of ZnO over In_2S_3 NSAs, which were in situ grown on fluorine-doped tin oxide glasses via a facile solvothermal process. The as-prepared photoanodes show dramatically enhanced performance for photoelectrochemical(PEC) water splitting, compared to single semiconductor counterparts. The optical and PEC properties of In_2S_3/ZnO NSAs have been optimized by modulating the thickness of the Zn O overlayer. After pairing with ZnO, the NSAs exhibit a broadened absorption range and an increased light absorptance over a wide wavelength region of 250–850 nm. The optimized sample of In_2S_3/ZnO-50 NSAs shows a photocurrent density of 1.642 m A cm^(-2)(1.5 V vs. RHE) and an incident photonto-current efficiency of 27.64% at 380 nm(1.23 V vs.RHE), which are 70 and 116 times higher than those of the pristine In_2S_3 NSAs, respectively. A detailed energy band edge analysis reveals the type-II band alignment of the In_2S_3/ZnO heterojunction, which enables efficient separation and collection of photogenerated carriers,especially with the assistance of positive bias potential, and then results in the significantly increased PEC activity.

Nanoforest-like CdS/TiO_2 heterostructure composites:Synthesis and photoelectrochemical application

In this study, YiO2 nanoforest films consisting of nanotubes have been synthesized by a simple hydrothermal method and a subsequent sintering technique. The hydrothermal reaction time is important for the controlling of the nanotube diameter and the specific surface area of holistic TiO2 films. When the hydrothermal process reaction time is up to 8 hours, the diameter of the nanotuhe is about 10 nm, and the specific surface area of TiO2 nanoforest films reaches the maximum. CdS nanoparticles are synthesized on TiO2 nanoforest films by the successive ionic layer adsorption and reaction （SILAR） technique. The transmission electron microscope （TEM） and energy dispersive x-ray spectroscopy （EDX） mapping results verify that TiOz/CdS heterostructures are realized. A significant red-shift of the absorption edge from 380 nm to 540 nm can be observed after the pure TiO2 film is sensitized by CdS nanoparticles. Under irradiation of light, the current density of the optimal TiO2/CdS photoanode is 2.30 mA.cm-2 at 0 V relative to the saturated calomel electrode （SCE）, which is 6 times stronger than that of the pure TiO2 photoanode. This study suggests that the TiO2 nanoforest consisting of interlinked pony-size nanotubes is a promising nanostructure for photoelectrochemical.

Advances in Z-scheme semiconductor photocatalysts for the photoelectrochemical applications: A review

With continuous consumption of nonrenewable energy,solar energy has been predicted to play an essential role in meeting the energy demands and miti gating environmental issues in the future.Despite being green,clean and pollution-free energy,solar energy cannot be adopted directly as it cannot provide sufficiently high energy density to work in the absence of machinery.Thus,it is necessary to develop an effective strategy to convert and store solar energy into chemical energy to achieve social sustainable development using solar energy as the main power source.Photocatalysis,in which semi conductor photocatalysts play a key role,is one of the most promising can didates for realising the effective utilisation of sunlight in a green,low-cost and environmentally friendly method.The photocatalytic efficiency of photo catalysts is considerably influenced by their compositions.Among the various heterostructures,Z-scheme heterojunction is one of the most interesting ar chitecture due to its outstanding performance and excellent artificial imitation of photosynthesis.Z-scheme photocatalysts have attracted considerable at tention in the past few decades.Herein,we review contemporary Z-scheme systems,with a particular focus on mechanistic breakthroughs,and highlight current state-of-the-art systems.Z-type photocatalysts are classified as tradi tional,all-solid-state,direct Z-schemes and S-scheme photocatalysts.The morphology,characterisation and working mechanism of each type of Z-scheme are discussed in detail.Furthermore,the applications of Z-scheme in photoelectrochemical water splitting,nitrogen fixation,pollutant degrada tion and carbon dioxide reduction are illustrated.Finally,we outline the main challenges and potential advances in Z-scheme architectures,as well as their future development directions.