氧化锌基梯型异质结光催化剂

随着工业的快速发展和化石燃料的过度开发使用,能源危机和环境污染日益严重.光催化技术在能源与环境领域具有良好的应用前景,是人类社会可持续发展的有效策略之一.传统氧化锌(ZnO)光催化剂因其无毒性、良好生物相容性和低成本而备受关注.然而,ZnO光催化性能受限于光生载流子复合严重和光生电子还原能力弱等问题.常规的改性方法,包括原子掺杂、缺陷调控、助催化剂负载等,很难兼顾载流子分离效率和氧化还原能力.相较而言,构建梯型异质结可以较好地解决上述问题.梯型异质结界面处的内建电场可以促进光生载流子的高效分离和转移,同时保留光催化体系最强的氧化还原能力,从而实现更高效的光催化反应.然而,尽管已有大量关于ZnO基梯型异质结的研究工作被陆续发表,却很少有评论性文章对该领域进行综述.因此,有必要对ZnO基梯型光催化剂的研究成果进行总结,并为这一研究方向的发展提供及时的指导.本文首先介绍了异质结的发展历程,讨论了II型异质结、传统Z型体系、全固态Z型异质结的光催化反应机理,并在此基础上指出了它们在热力学上的挑战.其次,深入分析了梯型异质结的理论基础,包括还原型半导体和氧化型半导体的选择,相互接触后的电子转移,梯型异质结中内建电场的形成,以及光激发后梯型异质结中光生载流子的分离和迁移,并诠释了梯型异质结在促进电荷载流子分离以及增强光催化体系的氧化还原能力方面的突出优势.此外,阐明了ZnO基梯型异质结的分类和设计原理.除了常见的ZnO基梯型n-n异质结,还讨论了以Zn O为还原型半导体的梯型n-p异质结以及以ZnO为氧化型半导体的梯型p-n异质结.归纳了目前ZnO基梯型异质结光催化剂的制备方法,包括水/溶剂热法、共沉淀法和静电自组装法等,剖析了这些制备方法的优缺点以及所制备的ZnO基梯型异质结的界面性质.概述了以ZnO基梯型异质结为代表的梯型异质结的表征技术,包括原位辐照X射线光电子能谱、开尔文探针力显微镜、电子顺磁共振波谱和第一性原理计算.总结了ZnO基梯型异质结近年来在不同光催化应用领域的研究进展,包括光催化环境修复、制氢、制备双氧水、二氧化碳还原、杀菌、固氮等.最后,对ZnO基梯型异质结的未来发展进行了展望,提出了其所面临的机遇与挑战,希望能为该领域带来新的启示.

Electrospun Semiconductor-Based Nano-Heterostructures for Photocatalytic Energy Conversion and Environmental Remediation:Opportunities and Challenges

Harvesting solar energy to drive the semiconductor photocatalysis offers a promising tactic to address ever-growing challenges of both energy shortage and environmental pollution.Design and synthesis of nano-heterostructure photocatalysts with controllable components and morphologies are the key factors for achieving highly efficient photocatalytic processes.Onedimensional(1D)semiconductor nanofibers produced by electrospinning possess a large ratio of length to diameter,high ratio of surface to volume,small grain sizes,and high porosity,which are ideally suited for photocatalytic reactions from the viewpoint of structure advantage.After the secondary treatment of these nanofibers through the solvothermal,gas reduction,in situ doping,or assembly methods,the multi-component nanofibers with hierarchical nano-heterostructures can be obtained to further enhance their light absorption and charge carrier separation during the photocatalytic processes.In recent years,the electrospun semiconductorbased nano-heterostructures have become a“hot topic”in the fields of photocatalytic energy conversion and environmental remediation.This review article summarizes the recent progress in electrospinning synthesis of various kinds of high-performance semiconductor-based nano-heterostructure photocatalysts for H2 production,CO_(2) reduction,and decomposition of pollutants.The future perspectives of these materials are also discussed.

Prolonging charge-separation states by doping lanthanide-ions into {001}/{101} facets-coexposed TiO_(2) nanosheets for enhancing photocatalytic H_(2) evolution

Ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets have attracted considerable attention because of their high photocatalytic activity.However,the charge-separated states in the TiO_(2)nanosheets must be extended to further enhance their photocatalytic activity for H_(2)evolution.Herein,we present a successful attempt to selectively dope lanthanide ions into the{101}facets of ultrathin TiO_(2)nanosheets with coexposed{001}/{101}facets through a facile one-step solvothermal method.The lanthanide doping slightly extended the light-harvesting region and markedly improved the charge-separated states of the TiO_(2)nanosheets as evidenced by UV-vis absorption and steady-state/transient photoluminescence spectra.Upon simulated sunlight irradiation,we observed a 4.2-fold enhancement in the photocatalytic H_(2)evolution activity of optimal Yb^(3+)-doped TiO_(2)nanosheets compared to that of their undoped counterparts.Furthermore,when Pt nanoparticles were used as cocatalysts to reduce the H_(2)overpotential in this system,the photocatalytic activity enhancement factor increased to 8.5.By combining these results with those of control experiments,we confirmed that the extended charge-separated states play the main role in the enhancement of the photocatalytic H_(2)evolution activity of lanthanide-doped TiO_(2)nanosheets with coexposed{001}/{101}facets.

One-step hydrothermal synthesis of S-defect-controlled ZnIn_(2)S_(4) microflowers with improved kinetics process of charge-carriers for photocatalytic H_(2) evolution

Engineering lattice defects in two-dimensional(2 D) sulfide semiconductors has been accepted as an effective strategy to enhance the efficiency of the solar-to-fuels conversion.Although many researches have proven the lattice defect-mediated photocatalytic activity of ZnIn_(2)S_(4),the artificial control of Sdefects for optimizing the charge-carrier kinetics process in ZnIn_(2)S_(4) has long been a challenging task.Herein,we report a facile one-step method to modulate the lattice S-content of ZnIn_(2)S_(4) microflowers(MFs) only through adjusting the used amount of S-precursor in the hydrothermal solution that contains the metal precursors with a fixed Zn/In stoichiometric ratio at 1:2.We also demonstrated that the Svacancies at the In facets were the main type of lattice defects in the formed ZnIn_(2)S_(4) MFs,which could enhance both the separation and migration processes of the photoinduced charge-carriers due to the existence of discrete defect energy-levels(DELs) and the reduced effective mass of electrons,as evidenced by the first-principles calculations and the electron spectra analyses.The ZnIn_(2)S_(4) MFs with the optimal content of S-vacancy obtained by a hydrothermal treatment of the precursors with the Zn/In/S stoichiometric ratio of 1:2:8 possessed the long-lived photoinduced electron(~94.64 ns) for contributing to the photo-physical and-chemical processes.Thus,upon visible light irradiation,the H_(2)-evolution rate of this sample reached ~2.40 mmol h^(-1) g^(-1) with an apparent quantum efficiency of ~0.16% at 420 nm even though only using 5 mg of photocatalysts without any cocatalysts.

Reinforcement Learning Behavioral Control for Nonlinear Autonomous System

Behavior-based autonomous systems rely on human intelligence to resolve multi-mission conflicts by designing mission priority rules and nonlinear controllers.In this work,a novel twolayer reinforcement learning behavioral control(RLBC)method is proposed to reduce such dependence by trial-and-error learning.Specifically,in the upper layer,a reinforcement learning mission supervisor(RLMS)is designed to learn the optimal mission priority.Compared with existing mission supervisors,the RLMS improves the dynamic performance of mission priority adjustment by maximizing cumulative rewards and reducing hardware storage demand when using neural networks.In the lower layer,a reinforcement learning controller(RLC)is designed to learn the optimal control policy.Compared with existing behavioral controllers,the RLC reduces the control cost of mission priority adjustment by balancing control performance and consumption.All error signals are proved to be semi-globally uniformly ultimately bounded(SGUUB).Simulation results show that the number of mission priority adjustment and the control cost are significantly reduced compared to some existing mission supervisors and behavioral controllers,respectively.

Reversing free-electron transfer of sulfide cocatalyst for exceptional photocatalytic H_(2)evolution

Recently,Yu and co-workers deeply explore the potential impact of free electron transfer between co-catalysts and photocatalyst carriers on H_(2)evolution efficiency of active sites over MoS_(2+x).They pro-pose an electron-reversal tactics to evade the unexpected electron transfer and synchronously regulate the above transfer in a beneficial orientation for weakening hydrogen adsorption on S sites.Herein,this highlight not only discusses and summarizes the essences of electron reversal and the optimized H ad-sorption/desorption mechanism,but also emphasizes the significance of femtosecond transient absorp-tion spectroscopy(fs-TAS)and in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS)for revealing charge transfer dynamics and processes.We anticipate that this highlight can disseminate a new per-spective on the roles of photocatalyst carriers in improving cocatalytic H_(2)-production kinetics.

A DFT study on Pt single atom loaded COF for efficient photocatalytic CO_(2)reduction

Photocatalytic CO_(2)reduction provides a promising strategy for the alleviation of greenhouse effect and energy shortage problem.Metal single atom modification is an effective method to improve the CO_(2)reduction performance of covalent organic framework(COF)photocatalysts,while the intrinsic mechanism is not revealed in depth.Herein,a Pt-COF photocatalytic system was constructed by embedding Pt single atom in TFPT-TMT-COF(TFPT:1,3,5-tris(4-formylphenyl)-triazine,TMT:2,4,6-trimethyl-1,3,5-triazine).Based on density functional theory(DFT)calculation,the geometric structure and electronic property of Pt-COF were investigated,and the CO_(2)adsorption and reduction reaction process on Pt-COF were simulated.The results show that the Pt atom can be steadily anchored in COF via the formation of Pt-N and Pt-C bonds.Moreover,there is strong electronic interaction between Pt and COF.The incorporation of Pt atom benefits the CO_(2)reduction activity of COF from multiple aspects:(ⅰ)reducing the band gap and improving light absorption;(ⅱ)enhancing CO_(2)adsorption and activating the CO_(2)molecule;(ⅲ)decreasing the energy barrier in the hydrogenation step of CO_(2)→COOH,thus facilitating CO_(2)conversion to CO;(ⅳ)inhibiting the hydrogenation of CO,thereby increasing the selectivity of CO.This work brings a novel insight into the excellent CO_(2)reduction performance of Pt modified COF,and provides useful references for the design of single atom photocatalysts.

Recent progress in CdS-based S-scheme photocatalysts

Photocatalytic technology with sunlight as driving force can convert solar energy into other energy sources for storage and further use.Cadmium sulfide(CdS),as a typical reducing semiconductor of metal sulfides,represents an interesting research hotspot in photocatalysis due to its suitable bandgap(2.4 eV)for utilizing visible light and strong reducing ability for inducing surface catalytic reactions.Unfortunately,the photocatalytic performance of CdS is still limited by its fast carrier recombination and serious pho-tocorrosion.So far,CdS semiconductor has been widely developed as a typical reducing photocatalyst in constructing novel S-scheme heterojunction to overcome the above drawbacks.In this review,the de-sign concepts,basic principles,and charge transfer characteristics of CdS-based S-scheme heterojunction photocatalysts have been comprehensively introduced.Several advanced and effective characterization methods for studying the mechanism of CdS-based S-scheme heterojunction are analyzed in detail.Fur-thermore,we also summarize the typical applications of CdS-based S-scheme heterojunctions for water splitting,CO_(2) reduction,pollutant degradation,etc.Eventually,according to the current investigation sta-tus,some drawbacks in the current synthetic strategy,mechanism exploration,and application prospect of CdS-based S-scheme heterojunction are proposed,which need to be addressed by further expansion and innovative research.

Multi-agent reinforcement learning behavioral control for nonlinear second-order systems

Reinforcement learning behavioral control(RLBC)is limited to an individual agent without any swarm mission,because it models the behavior priority learning as a Markov decision process.In this paper,a novel multi-agent reinforcement learning behavioral control(MARLBC)method is proposed to overcome such limitations by implementing joint learning.Specifically,a multi-agent reinforcement learning mission supervisor(MARLMS)is designed for a group of nonlinear second-order systems to assign the behavior priorities at the decision layer.Through modeling behavior priority switching as a cooperative Markov game,the MARLMS learns an optimal joint behavior priority to reduce dependence on human intelligence and high-performance computing hardware.At the control layer,a group of second-order reinforcement learning controllers are designed to learn the optimal control policies to track position and velocity signals simultaneously.In particular,input saturation constraints are strictly implemented via designing a group of adaptive compensators.Numerical simulation results show that the proposed MARLBC has a lower switching frequency and control cost than finite-time and fixed-time behavioral control and RLBC methods.

Behavioral control task supervisor with memory based on reinforcement learning for human-multi-robot coordination systems

In this study,a novel reinforcement learning task supervisor(RLTS)with memory in a behavioral control framework is proposed for human–multi-robot coordination systems(HMRCSs).Existing HMRCSs suffer from high decision-making time cost and large task tracking errors caused by repeated human intervention,which restricts the autonomy of multi-robot systems(MRSs).Moreover,existing task supervisors in the null-space-based behavioral control(NSBC)framework need to formulate many priority-switching rules manually,which makes it difficult to realize an optimal behavioral priority adjustment strategy in the case of multiple robots and multiple tasks.The proposed RLTS with memory provides a detailed integration of the deep Q-network(DQN)and long short-term memory(LSTM)knowledge base within the NSBC framework,to achieve an optimal behavioral priority adjustment strategy in the presence of task conflict and to reduce the frequency of human intervention.Specifically,the proposed RLTS with memory begins by memorizing human intervention history when the robot systems are not confident in emergencies,and then reloads the history information when encountering the same situation that has been tackled by humans previously.Simulation results demonstrate the effectiveness of the proposed RLTS.Finally,an experiment using a group of mobile robots subject to external noise and disturbances validates the effectiveness of the proposed RLTS with memory in uncertain real-world environments.

A flexible conductive hybrid elastomer for high-precision stress/strain and humidity detection

Flexible and environment-responsive materials are essential for a large number of applications from artificial skin to wearable devices. The present study develops a flexible, ultra-low cost conductive hybrid elastomer(CHE), which possesses high responsive capabilities to stress/strain and humidity. CHE was composed of polydimethylsiloxane(PDMS) and starch hydrogel(SH), enabling great elasticity(56 kPa),high conductivity(10^(-2)S/m) and high sensitivity to external stimuli(gauge factor of CHE under stress and strain are 0.71 and 2.22, respectively, and sensitivity to humidity is 1.2 × 10^(-6)S/m per RH%). These properties render CHE a promising candidate for artificial skin and wearable electronics applications of continuously monitoring environmental information.

Enhancement of filtration efficiency by electrical charges on nebulized particles

There have been few investigations of effects of electrical charge, carried by lab-generated particles, on filtration efficiency testing. Here, we measured the elementary charge on particles and the fraction of particles carrying that charge with a combined electrometer, differential mobility analyzer, and scanning mobility particle sizer. A typical solid NaCI aerosol and liquid diethylhexyl sebacate （DEHS） aerosol were generated with Collison and Laskin nebulizers, respectively. Our experimental results showed that NaCI aerosols carried more charge after aerosol generation. The average net elementary charge per particle was approximately 0.07. The NaCI aerosol was overall positively charged but contained a mixture of neutral and charged particles. Individual particles could carry at most four elementary charges. According to constant theorem, we speculated that original NaC1 aerosol contained 17% neutral, 45% positive-, and 38% negative-charged particles in the diameter range from 30 to 300nm. A Kr-85 neutralizer was used to decrease the charge on the NaCI particles. Our results indicated that the DEHS aerosol was electrically neutral. The effects of electric charge on particle collection by electret and electroneutral high efficiency particulate air （HEPA） filters were analyzed. Theoretical calculations suggested that charges on original NaCI aerosol particles enhanced the filtration efficiency of HEPA filters,

Sulfonate-Functionalized Polyoxovanadate-Based Metal-Organic Polyhedra for Enhanced Proton Conduction via the Synergy of Linker and Metal Cluster Vertex

Metal-organic polyhedra(MOPs)have emerged as novel porous platforms for proton conduction,however,the concerted employment of both linker and metal cluster vertex is rarely applied for the fabrication of MOPs-based high conducting materials.Herein we report the synthesis of sulfonate-functionalized polyoxovanadate-based MOPs for enhanced proton conduction via the synergistic effect from linker and metal cluster node.MOPs 1 and 2 exhibit octahedral cage configuration constructed from{V_(5)O_(9)Cl}vertex and 5-sulfoisophthalate linker.Owing to the ordered packing of octahedral cages along three axes,3D interpenetrated open channels that are lined with high-density sulfonates are thus formed within 2.Coupled with the proton-conductive{V_(5)O_(9)Cl}vertexs as well as protonated counterions,an extensive H-bonded network is therefore generated for facile proton transfer.2 exhibits high proton conductivity of 3.02×10^(-2)S cm^(-1)at 65℃under 90%RH,recording the highest value for MOPs pellet sample.This value is enhanced~1order of magnitude compared with that of carboxylate-functionalized analogue 3,clearly illustrating the advantage of combining linker and metal cluster node for enhanced proton conduction.This work will further promote the exploitation of high proton conductive MOPs-based materials by the synergy design strategy.

Impact of solids on biphasic biodegradation of phenanthrene in the presence of hydroxypropyl-β-cyclodextrin(HPCD)

The consequence of polycyclic aromatic hydrocarbons(PAHs)in the environment is of great concern.The hydrophobic properties of PAHs significantly impact phase distribution causing limited bioavailability.Enhanced biodegradation has been extensively carried out by surfactants and the redeployment effect was recognized.However,the quantitative relationship concerning the impact of solids was rarely reported.A batch of biphasic tests were carried out by introducing Mycobacterium vanbaalenii PYR-1 and hydroxypropyl-β-cyclodextrin(HPCD)into a mixture of phenanthrene solution and various glass beads(GB37-63,GB105-125,and GB350-500).The comparative results demonstrated that HPCD had little effect on microbial growth and was not degradable by bacterium.A model was proposed to describe the biodegradation process.The regression results indicated that the partition coefficient kd(1.234,0.726 and 0.448 L·g–1)and the degradation rate k(0 mmol·L^(–1):0.055,0.094,and 0.112;20 mmol·L^(–1):0.126,0.141,and 0.156;40 mmol·L^(–1):0.141,0.156 and 0.184 d^(–1))were positively and negatively correlated with the calculated total surface area(TSA)of solids,respectively.Degradation enhanced in the presence of HPCD,and the enhancing factor f was calculated(20 mmol·L^(–1):15.16,40.01,and 145.5;40 mmol·L^(–1):13.29,37.97,and 138.4),indicating that the impact of solids was significant for the enhancement of biodegradation.

Switchable optical nonlinear properties of W_(18)O_(49) nanowires by Ag nanoparticles supported

During the past decades,nonlinear optical（NLO）materials have attracted special interest because of their potential applications in photonic devices,such as optical switching,frequency conversion and electro-optic modulators.Among the finding ways to obtain excellent NLO materials with both large NLO response and short response time,

发电机组的自启动装置及其维护

数据中心普遍应用的发电机组,在市电中断时能自主启动并输出优良的电能代替市电供设备工作,其自启动装置是重要的运作机构。应读者咨询,本文介绍它的运行过程和维护要点。