摘要：Charge separation and transformation are some of the key requirements for high-efficiency photocatalysis. The photocatalytic reaction mechanism provides a guideline for the development and commercialization of high-efficiency photocatalysts. In this study, we designed and favorably synthesized BMO@BOC heterojunctions via a facile solvothermal route and applied the heat treatment method for application in high-efficiency photocatalytic NO removal. More importantly, both continuous stream and intermittent stream methods with in situ diffuse reflectance infrared Fourier transform spectroscopy were applied to intuitively and dynamically investigate the adsorption process and oxidation process of NO removal over the photocatalyst surface. The intermediate products(NO-, NO2-, and NO2) were explicitly detected in both the adsorption process and oxidation process, whilst the final product(NO3-) appeared only in the oxidation process, owing to the separation, migration, and conversion of photoinduced electron-hole pairs.

摘要：The catalytic hydrogenation of halonitroarenes to haloanilines is a green and sustainable process for the production of key nitrogen-containing intermediates in fine chemical *** hydrogenation poses a significant challenge,which requires the rational design of the catalysts with proper hydrogenation ability for nitro group and simultaneously preventing dehalogenation of halogen ***,a highly effective Rh@Al_(2)O_(3)@C single-atom catalyst(SAC)was developed for the hydrogenation of m-chloronitrobenzene(m-CNB)to m-chloroaniline(m-CAN),through an in-situ grafting of metal during the assembly of MIL-53(Al),followed by confined *** characterizations reveal an exquisite structure of the Rh@Al_(2)O_(3)@C,containing atomically dispersed Rh sites onto Al_(2)O_(3) confined by the amorphous *** five-coordinated aluminum(Al^(Ⅴ))species are essential for achieving the atomic dispersion of Rh atoms,providing the unsaturated coordinative sites for *** to the benchmark Rh/γ-Al_(2)O_(3) and Rh/C nanocatalysts,the Rh@Al_(2)O_(3)@C SAC affords an excellent turnover frequency of 2317 molm-CNB·molRh^(–1)·h^(–1),the highest value to date in heterogeneous catalyst systems for the hydrogenation of m-CNB at 313 K and 20 bar H2,together with a sustained selectivity to m-CAN(~98%)during five consecutive *** superior catalytic performance of the Rh@Al_(2)O_(3)@C is attributed to a proper modulation of electronic structure of hydrogenation metal by forming SAC,together with an enhanced accessibility of acid function sites.

摘要：Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource ***,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic ***,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction *** transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area *** function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance ***,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform *** functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and *** Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 *** study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.

摘要：The development of high-performance solid polymer electrolytes is crucial for producing all-solid-state lithium metal batteries with high safety and high energy ***,the low ionic conductivity of solid polymer electrolytes and their unstable electrolyte/electrode interfaces have hindered their widespread *** address these critical challenges,a strong Lewis acid(aluminum fluoride(AIF_(3)))with dual functionality is introduced into poly(ethylene oxide)(PEO)-based polymer *** AlF;facilitates the dissociation of lithium salt,increasing the iontransfer efficiency due to the Lewis acid-base interaction;further the in-situ formation of lithium fluoride-rich interfacial layer is promoted,which suppresses the uneven lithium deposition and continuous undesired reactions between the Li metal and PEO *** from our rational design,the symmetric Li/Li battery with the modified electrolyte exhibits much longer cycling stability(over 3600 h)than that of the pure PEO/lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)electrolyte(550 h).Furthermore,the all-solid-state LiFeP04 full cell with the composite electrolyte displays a much higher Coulombic efficiency(98.4%after 150 cycles)than that of the electrolyte without the AlF;additive(63.3%after 150 cycles)at a large voltage window of 2.4-4.2 V,demonstrating the improved interface and cycling stability of solid polymer lithium metal batteries.

摘要：非晶合金是非晶材料家族中的新成员,由于缺乏原子排列长程有序特征,具有独特的性能和广泛应用前景.然而,非晶合金的形成、成分设计和形变问题在该领域长期未得到解决,制约着新型非晶合金的高效开发.传统上,多组元非晶合金的成分设计主要遵循相图研究范式,以温度调控为出发点,确定低液相线的成分为落脚点,尤其强调深共晶成分.然而,对于缺乏相图的多组元体系则力所不及,亟需新的理论突破.本文综述了非晶转变中的热力学与动力学基本规律,重点探讨了热力学与动力学性质之间的关联性,尤其是梳理了材料熔化熵与熔点粘度、熔点等多个非晶形成经典参量之间的内在关联,提出并论证了熔化熵和振动熵为非晶形成的关键热力学参量,可有效指导高性能非晶合金的设计和表征.结合实际应用中对非晶材料的工程要求,讨论了化学成分调控对非晶合金剪切带的萌生密度和扩展稳定性的影响,并总结了在单调加载和疲劳加载条件下剪切带行为对非晶合金断裂过程的作用.最后展望了振动熵和构型熵之间争议问题,提出未来工作中需要发展具有物理意义玻璃形成能力指标和可靠数据库的需求,混合加载模式下的韧性以及疲劳和韧性之间的权衡等问题.本文为进一步建立高性能非晶材料成分设计路径提供了参考与指导.

摘要：开发高熵硼化物材料的功能特性对于拓宽其在极端环境中的潜在应用至关重要.为此,本文通过调控材料的组分开发出具有高效催化性能的高熵二硼化物(HEB_(2))纳米颗粒:首先基于对HEB_(2)的尺寸差异因子、混合焓以及体系自蔓延燃烧模式的理论分析,我们采用一种简便、快速、低成本的燃烧合成方法合成了6种不同组分的HEB_(2)纳米颗粒;然后,通过对材料的组分进行调控实现了HEB_(2)纳米颗粒活化过硫酸盐降解抗生素的高效催化能力(四环素的最高去除效率可达93.5%).不同吸附位点的吸附能和差分电荷密度的第一性原理计算结果进一步证实了HEB_(2)优异的催化性能主要归因于Ti组元,而非高熵效应.此外,基于检测到的活性氧和计算的反应能垒,我们提出了HEB_(2)活化过硫酸盐降解抗生素的潜在催化机理.本研究不仅为HEB_(2)高效催化降解抗生素的组分设计提供了理论依据,而且显示出HEB_(2)在去除自然水体中新污染物方面的潜在应用前景.

摘要：Feasible construction of cathode materials with highly dispersed active sites can extend the tri‐ple‐phase boundaries,and therefore leading to enhanced electrode kinetics for CO_(2) electrolysis in solid oxide electrolysis cell(SOEC).Herein,highly dispersed nickel species with low loading(1.0 wt%)were trapped within the La_(0.8)Sr_(0.2)FeO_(3)–δ‐Ce_(0.8)Sm_(0.2)O_(2)–δvia a facial mechanical milling ap‐proach,which demonstrated excellent CO_(2) electrolysis *** highly dispersed nickel species can significantly alter the electronic structures of the LSF‐SDC without affecting its porous network and facilitate oxygen vacancy formation,thus greatly promote the CO_(2) electrolysis perfor‐*** highest current density of 1.53 A·cm^(-2) could be achieved when operated under 800℃ at 1.6 V,which is about 91%higher than the LSF‐SDC counterpart.

摘要：Perovskite SrVO_(3) has been investigated as a promising lithium storage anode where the V cation plays the role of the redox center,combining excellent cycle stability and safe operating potential versus Li metal plating,with limited ***,we demonstrate the possibility to boost the lithium storage properties,by reducing the non-redox active Sr cation content and fine-tuning the O anion vacancies while maintaining a non-stoichiometric Sr_(x)VO_(3-δ) perovskite *** investigations suggest that Sr vacancy can work as favorable Li^(+) storage sites and preferential transport channels for guest Li^(+) ions,contributing to the increased specific capacity and rate *** contrast,inducing O anion vacancy in Sr_(x)VO_(3-δ) can improve rate performance while compromising the specific *** experimental results confirm the enhancement of specific capacities by fine adjusting the Sr and O vacancies,with a maximum capacity of 444 mAh g^(-1) achieved with Sr_(0.63)VO_(3-δ),which is a 37%increase versus stoichiometric SrVO_(3).Although rich defects have been induced,Sr_(x)VO_(3-δ) electrodes maintain a stable perovskite structure during cycling versus a LiFePO_(4) cathode,and the full-cell could achieve more than 6000 discharge/charge cycles with 80%capacity *** result highlights the possibility to use the cation defective-based engineering approach to design high-capacity perovskite oxide anode materials.

摘要：Development of efficient heterostructured photocatalysts that respond to visible light remains a considerable *** herein show the synthesis of ZnIn2S4/carbon quantum dot hybrid photocatalysts with flowerlike microspheres via a facile solvothermal *** ZnIn2S4/carbon quantum dot flowerlike microspheres display enhanced photocatalytic and photoelectrochemical activity compared with that of pure *** a content of only 0.5 wt%carbon quantum dots,93%of Cr(VI)is reduced under visible‐light irradiation at 40 *** a co‐catalyst,the carbon quantum dots improve the light absorption and lengthen the lifetime of charge carriers,consequently enhancing the photocatalytic and photoelectrochemical activity.

摘要：Rational design and controllable synthesis of efficient electrocatalysts for water oxidation is of significant importance for the development of promising energy conversion systems, in particular integrated photoelectrochemical water splitting devices. Cobalt oxide(Co3O4) nanostructures with mixed valences(Ⅱ,Ⅲ)have been regarded as promising electrocatalysts for the oxygen evolution reaction(OER). They are able to promote catalytic support of OER but with only modest activity. Here, we demonstrate that the OER performance of cubic Co3O4 electrocatalyst is obviously improved when they are anchored on delaminated two-dimensional(2D) Ti3C2 MXene nanosheets. Upon activation the overpotential of the hybrid catalyst delivers 300 m V at a current density of 10 m A cm(2) in basic solutions, which is remarkably lower than those of Ti3C2 MXene and Co3O4 nanocubes. The strong interfacial electrostatic interactions between two components contribute to the exceptional catalytic performance and stability. The enhanced OER activity and facile synthesis make these Co3O4 nanocubes-decorated ultrathin 2D Ti3C2 MXene nanosheets useful for constructing efficient and stable electrodes for high-performance electrochemical water splitting.