含氢空位氢化金刚石2维原子晶体体系与硫酸吲哚酚和水分子相互作用的第一性原理计算

基于立方金刚石晶体结构构建了2种2维原子晶体:氢化立方金刚石(hydrogenated cubic diamond,HCD)和含氢空位氢化立方金刚石(hydrogen vacancy-HCD,Hv-HCD);将含氢空位氢化立方金刚石与单层六方氮化硼(h-BN)和石墨烯(graphene,G)组装构建了2种2维原子晶体范德华异质结构:h-BN/Hv-HCD和G/Hv-HCD.根据第一性原理,对含氢空位氢化立方金刚石2维原子晶体体系、硫酸吲哚酚和水分子的Fukui函数进行了计算.研究结果显示,含氢空位氢化立方金刚石2维原子晶体体系的氢空位碳原子具有较大的f+(r)和f-(r)值,表明氢空位碳原子的亲电和亲核反应趋势较为显著.有关能量效应的计算结果表明:水分子与含氢空位氢化立方金刚石2维原子晶体体系的氢空位碳原子形成氢键;硫酸吲哚酚分子在氢空位碳原子位点发生化学分解,生成3-吲哚酮和二氧化硫,原磺酸基羟基与氢空位碳原子结合形成醇羟基.该体系可以作为基于2维原子晶体研发生物活性分子、人体血液毒素分子吸附清除以及检测分析核心材料的参考依据.

Vacancy engineering mediated hollow structured ZnO/ZnS S-scheme heterojunction for highly efficient photocatalytic H_(2) production

Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.

氢化空位的基本性质及其对金属力学行为的影响

金属和合金材料中广泛存在着氢脆现象,即由于氢的渗入使得材料的塑性变形能力显著下降,导致材料倾向于发生脆性或准脆性断裂。尽管氢诱发材料失效的问题被研究了很多年,但微观机理一直存在着广泛争议。本文以近年来的研究结果为基础,提出了"氢化空位"的概念(即氢-空位复合体),认为其是氢致材料失效初期微观结构的最小载体。利用多尺度模拟并结合实验测试,揭示出氢化空位不同于空位的特殊性质,研究了氢环境下在塑性变形中氢化空位的产生、聚集并经过长时间演化形成纳米孔洞的过程,构建出原子尺度事件与微观失效之间的联系。该研究丰富了对氢脆微观机制的理解,同时氢化空位的概念也为揭示氢环境下的其它特殊力学行为提供了思路。

Engineering vacancies for solar photocatalytic applications

In contrast to the exploration of novel photocatalytic materials,vacancy engineering of traditionalphotocatalysts comprising earth‐abundant elements represents an effective method for enhancingphotocatalytic performance without introducing alien elements.This minireview analyzes the latestprogress in engineering vacancies in photocatalysts,remarks on state‐of‐the‐art characterizationtechniques for vacancies,and reviews the formation chemistry and fundamental benefits of anionand cation vacancies in typical photocatalysts.Although knowledge of these vacancies is increasing,challenges remain in this field,and possible further research is therefore also discussed.

Determining number of sites on ceria stabilizing single atoms via metal nanoparticle redispersion

Single atom catalysts have recently attracted interest due to their maximization of the utilization of expensive noble metals as well as their unique catalytic properties. Based on its surface atomic properties, CeO2 is one of the most common supports for stabilizing single metal atoms. Many single atom catalysts are limited in their metal contents by the formation of metal nanoparticles once the catalyst support capacity for single atoms has been exceeded. Currently, there are no direct measurements to determine the capacity of a support to stabilize single atoms. In this work we develop a nanoparticle-based technique that allows for quantification of that capacity by redispersing Ru nanoparticles into single atoms and taking advantage of the different catalytic properties of Ru single atoms and nanoparticles in the CO2 hydrogenation reaction. This method avoids complications in metal loading caused by counterions in incipient wetness impregnation and can eventually be applied to a variety of different metals. Results using this technique follow trends in oxygen vacancy concentration and surface oxygen content and show promise as a new method for quantifying support single atom stabilization capacity.

A review of defect engineering in two‐dimensional materials for electrocatalytic hydrogen evolution reaction

The exploration of efficient and earth‐rich electrocatalysts for electrochemical reactions is critical to the implementation of large‐scale green energy conversion and storage techniques.Two‐dimensional(2D)materials with distinctive structural and electrochemical properties provide fertile soil for researchers to harvest basic science and emerging applications,which can be divided into metal‐free materials(such as graphene,carbon nitride and black phosphorus)and transition metal‐based materials(such as halogenides,phosphates,oxides,hydroxides,and MXenes).For faultless 2D materials,they usually exhibit poor electrochemical hydrogen evolution reaction(HER)activity because only edge sites can be available while the base surface is chemically inactive.Defect engineering is an effective strategy to generate active sites in 2D materials for improving electrocatalytic activity.This review presents feasible design strategies for constructing defect sites(including edge defects,vacancy defects and dopant derived defects)in 2D materials to improve their HER performance.The essential relationships between defect structures and electrocatalytic HER performance are discussed in detail,providing valuable guidance for rationally fabricating efficient HER electrocatalysts.The hydrogen adsorption/desorption energy can be optimized by constructing defect sites at different locations and by adjusting the local electronic structure to form unsaturated coordination states for efficient HER.

Activation of small molecules over praseodymium-doped ceria

Praseodymium can modify the properties of ceria (CeO2), changing the electronic structure, reducibility and catalytic behavior. Oxygen vacancies in the ceria-based samples can activate C–O and C–H bonds of small molecules such as CO2 and propane. Partially reduced Pr/CeO2-x can selectively activate C–H of propane, giving a propylene selectivity of ca. 75% at a propane conversion of 5% to 10%. Excess reduction of Pr/CeO2-x induces coking reactions during propane dehydrogenation, resulting in fast catalyst deactivation.

Engineering oxygen vacancy on rutile TiO_2 for efficient electron-hole separation and high solar-driven photocatalytic hydrogen evolution

Oxygen vacancy（VO） plays a vital role in semiconductor photocatalysis. Rutile TiO2 nanomaterials with controllable contents of VO（0–2.18%） are fabricated via an insitu solid-state chemical reduction strategy, with color from white to black. The bandgap of the resultant rutile TiO2 is reduced from 3.0 to 2.56 e V, indicating the enhanced visible light absorption. The resultant rutile TiO2 with optimal contents of VO（2.07%） exhibits a high solar-driven photocatalytic hydrogen production rate of 734 μmol h-1, which is about four times as high as that of the pristine one（185 μmol h-1）. The presence of VOelevates the apparent Fermi level of rutile TiO2 and promotes the efficient electronhole separation obviously, which favor the escape of photogenerated electrons and prolong the life-time（7.6×103 ns） of photogenerated charge carriers, confirmed by scanning Kelvin probe microscopy, surface photovoltage spectroscopy and transient-state fluorescence. VO-mediated efficient photogenerated electron-hole separation strategy may provide new insight for fabricating other high-performance semiconductor oxide photocatalysts.

Sulfur defect-rich WS nanosheet electrocatalysts for N reduction

Seeking catalysts with high electrocatalytic activity for ambient-condition N2 reduction reaction (NRR) remains an ongoing challenge due to the chemical inertness of N2.Herein,defect-rich WS2 nanosheets (WS2-x) were designed as an efficient electrocatalyst for NRR,which were prepared via vulcanizing the oxygen-vacancy-rich tungsten oxide in a vacuum tube.The sulfur defects were conducive to the adsorption and activation of N2.In neutral electrolyte of 0.1 mol L^(-1)Na2SO_(4) at-0.60 V vs.reversible hydrogen electrode,such WS2-xoffered a high Faradaic efficiency of 12.1%with a NH3generation rate of 16.38μg h-1mg-1cat..