Electron-deficient ZnO induced by heterointerface engineering as the dominant active component to boost CO_(2)-to-formate conversion

Electrocatalytic CO_(2)-to-formate conversion is considered an economically viable process.In general,Zn-based nanomaterials are well-known to be highly efficient electrocatalysts for the conversion of CO_(2) to CO,but seldom do they exhibit excellent selectivity toward formate.In this article,we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency(FE)of 86%at−0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO_(2) to formate than pristine ZnO and ZnSnO3.In particular,the FEs of the C1 products(CO+HCOO−)exceed 98%over the potential window.The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d-band center,which results in moderate Zn-O hybridization of HCOO*and weakened Zn-C hybridization of competing COOH*,thus greatly boosting the HCOOH generation.Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO_(2) reduction.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Modified TiO_(2)/In_(2)O_(3) heterojunction with efficient charge separation for visible-light-driven photocatalytic CO_(2) reduction to C_(2) product

Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic CO_(2) conversion.Herein,a modified TiO_(2)/In_(2)O_(3)(R-P2 5/In_(2)O_(3-x)) type Ⅱ heterojunction composite with oxygen vacancies is designed for photocatalytic CO_(2) reduction,which exhibits excellent CO_(2) reduction activity,with a C_(2) selectivity of 56.66%(in terms of R_(electron)).In situ Fourier-transform infrared spectroscopy(DRIFTS) and time-resolved photoluminescence(TR-PL) spectroscopy are used to reveal the intermediate formation of the photocatalytic mechanism and photogenerated electron lifetime,respectively.The experimental characterizations reveal that the R-P25/In_(2)O_(3-x) composite shows a remarkable behavior for coupling C-C bonds.Besides,efficient charge separation contributes to the improved CO_(2) conversion performance of photocatalysts.This work introduces a type Ⅱ heterojunction composite photocatalyst,which promotes understanding the CO_(2) reduction mechanisms on heterojunction composites and is valuable for the development of photocatalysts.

Exploring catalytic behaviors of CoS_(2)-ReS_(2) heterojunction by interfacial engineering

Herein, a stable and efficient CoS_(2)-ReS_(2) electrocatalyst is successfully constructed by using the different molar ratios of CoS_(2) on ReS_(2). The size and morphology of the catalysts are significantly changed after the CoS_(2) is grown on ReS_(2), providing regulation of the catalytic activity of ReS_(2). Particularly, the optimized CoS_(2)-ReS_(2) shows superior electrocatalytic properties with a low voltage of 1.48 V at 20 mA cm^(-2) for overall water splitting in 1.0 M KOH, which is smaller than the noble metal-based catalysts(1.77 V at 20 mA cm^(-2)). The XPS, XAS, and theoretical data confirm that the interfacial regulation of ReS_(2) by CoS_(2) can provide rich edge catalytic sites, which greatly optimizes the catalytic kinetics and drop the energy barrier for oxygen/hydrogen evolution reactions. Our results demonstrated that interfacial engineering is an efficient route for fabricating high-performance water splitting electrocatalysts.

Oxygen-deficient SnO_(2)nanoparticles with ultrathin carbon shell for efficient electrocatalytic N_(2)reduction

For high-efficiency NH_(3)synthesis via ambient-condition electrohydrogenation of inert N_(2),it is pivotal to ingeniously design an active electrocatalyst with multiple features of abundant surfacial deficiency,good conductivity and large surface area.Here,oxygen-deficient SnO_(2)nanoparticles encapsulated by ultrathin carbon layer(d-SnO_(2)@C)are developed by hydrothermal deposition coupled with annealing process,as promising catalysts for ambient electrocatalytic N_(2)reduction.d-SnO_(2)@C exhibits high activity and excellent selectivity for electrocatalytic conversion of N_(2)to NH_(3)in acidic electrolytes,with Faradic efficiency as high as 12.7%at-0.15 V versus the reversible hydrogen electrode(RHE)and large NH_(3)yield rate of 16.68μg h^(-1)mgcat^(-1)at-0.25 V vs.RHE in 0.1 mol L^(-1)HCl.Benefiting from the structural superiority of enhanced charge transfer efficiency and optimized surface states,d-SnO_(2)@C also achieves excellent long-term stability.

晶格应变和异质界面工程协同促进铋基催化剂高效电催化CO_(2)还原生成甲酸

表面应力耦合异质结构是一种改善非均相催化剂催化性能的有效策略.它可以在调控催化剂电子结构的同时,促进电荷传输.一般来说,Bi基催化剂对CO_(2)电还原为甲酸的选择性高于ZnO,但是金属Bi的价格高于Zn.本文以十六烷基三甲基溴化铵为模板剂,通过一步水热法合成了一种具有多孔纳米片形貌的Bi_(2)O_(2)CO_(3)/ZnO异质结催化剂,用于高效电催化CO_(2)还原制备甲酸.在-1.0 V vs.RHE下,该催化剂展现出最大甲酸盐法拉第效率(92%),且在施加-1.2 V vs.RHE电压下甲酸盐偏电流密度为200 m A mg_(Bi)^(-1).更重要的是,对Bi的质量进行归一化发现,Bi_(2)O_(2)CO_(3)/ZnO的质量活度比纯Bi_(2)O_(2)CO_(3)的质量活度提升了3.1倍.通过X-射线光电子能谱和X-射线吸收谱测试表明,在该催化剂中,界面Zn原子电荷向Bi原子转移,形成了富电子的Bi_(2)O_(2)CO_(3)表面,有利于CO_(2)的捕获和活化;而异质结构引起的压缩应力有利于优化反应中间体的吸附能,二者协同提高了Bi_(2)O_(2)CO_(3)/ZnO电催化CO_(2)还原生成甲酸的选择性和活性.

Three-dimensional hierarchical Co(OH)F nanosheet arrays decorated by single-atom Ru for boosting oxygen evolution reaction

Electronic coupling with the support plays a crucial role in boosting the intrinsic catalytic activity of a single-atom catalyst.Herein,the three-dimensional(3D)hierarchical Co(OH)F nanosheet arrays modified by singleatom Ru(SA-Ru/Co(OH)F)are prepared by a facile one-step hydrothermal method under mild conditions,which exhibit excellent activity with an overpotential of 200 and 326 mV at 10 and 500 mA cm^(−2),respectively,as well as robust stability for oxygen evolution reaction(OER)in 1.0 mol L^(−1)KOH electrolyte.The study of electronic structures and surface chemical states before and after OER testing reveals that the strong electronic coupling between single-atom Ru and Co(OH)F induces the charge redistribution in SA-Ru/Co(OH)F and suppresses the excessive oxidation of Ru into higher valence state(more than+4)under high OER potential.This work provides a strategy to stabilize single-atom Ru by Co(OH)F that can enhance the activity and durability for OER under large current densities.

Storage Characteristics of LiNi_(0.8)Co_(0.1+X)Mn_(0.1-X)O_2 (X=0,0.03,0.06) Cathode Materials for Lithium Batteries

1 Results LiNi0.8Co0.1+xMn0.1-xO2 cathodes with x=0,0.03 and 0.06 were prepared by firing a mixture of stoichiometric amounts of LiOH·H2O and coprecipitated Ni0.8Co0.1+xMn0.1-x(OH)2 at 800 ℃ for 15 h.Using these powders,their storage characteristics upon exposure to air and electrolytes at 90 ℃ were compared before charging and after charging to 4.3 V with a variation of the storage time.As the Co content (x) increased in the cathode,both the Ni2+ content in the lithium 3a sites,and the contents of the ...