Construction of 3D porous Cu_(1.81)S/nitrogen-doped carbon frameworks for ultrafast and long-cycle life sodium-ion storage

Transition metal sulfides have great potential as anode mterials for sodium-ion batteries(SIBs)due to their high theoretical specific capacities.However,the inferior intrinsic conductivity and large volume variation during sodiation-desodiation processes seriously affect its high-rate and long-cyde performance,unbeneficial for the application as fast-charging and long-cycling SIBs anode.Herein,the three-dimensional porous Cu_(1.81)S/nitrogen-doped carbon frameworks(Cu_(1.81)S/NC)are synthesized by the simple and facile sol-gel and annealing processes,which can accommodate the volumetric expansion of Cu_(1.81)S nanoparticles and accelerate the transmission of ions and electrons during Na^(+)insertion/extraction processes,exhibiting the excellent rate capability(250.6 mA·g^(-1)at 20.0 A·g^(-1))and outstanding cycling stability(70% capacity retention for 6000 cycles at 10.0 A·g^(-1))for SIBs.Moreover,the Na-ion full cells coupled with Na_(3)V_(2)(PO_(4))_(3)/C cathode also demonstrate the satisfactory reversible specific capacity of 330.5 mAh·g^(-1)at 5.0 A·g^(-1)and long-cycle performance with the 86.9% capacity retention at 2.0 A·g^(-1)after 750 cycles.This work proposes a promising way for the conversionbased metal sulfides for the applications as fast-charging sodium-ion battery anode.

电催化二氧化碳与含氮小分子共还原的缺陷与界面工程

化石燃料的大量燃烧和利用造成日益严重的能源危机、全球气候变暖和环境污染,已成为人类面临的严峻挑战.因此,迫切需要开发可持续的能源存储和转换技术.其中,将二氧化碳(CO_(2))、氮气(N_(2))、硝酸盐(NO_(3)^(-))和亚硝酸盐(NO_(2)^(-))等广泛分布的小分子和环境污染物转化为高附加值的化学品和燃料受到了广泛关注.然而,工业合成方法通常需要高温高压等极为苛刻的条件并消耗大量的能量(如Haber-Bosch和Bosch-Meiser方法分别用于合成氨(NH3)和尿素),这加剧了能源危机和环境污染.因此,在常温常压下,由可再生的电能驱动的电化学催化小分子转化为高附加值化学品被认为是最有前途的能量储存和转化技术之一,它为缓解日益严重的环境问题和能源危机提供了契机.本文系统地总结了近年来在常温常压下电催化CO_(2)与含氮小分子(N_(2),NH_(3),NO_(2)^(-)和NO_(3)^(-))共还原合成高附加值的含氮肥料(如尿素)和化学品(如酰胺和胺等)的研究进展,尤其是缺陷化学和界面工程与催化活性/选择性之间的构效关系.首先,根据空间尺寸和来源介绍了缺陷的分类,阐述了界面和缺陷之间的内在联系,总结了掺杂、刻蚀、热处理等缺陷构建方法,以及电镜法和谱学法等缺陷表征手段.其次,系统地介绍了通过构建空位(尤其是氧空位)、异原子掺杂、设计单原子催化剂及双原子催化剂等缺陷设计策略来提升电催化碳-氮(C-N)偶联反应合成含氮有机物性能的最新研究进展,阐明了不同缺陷结构对催化剂电子结构和反应物/中间体吸附特征的调控作用.此外,归纳了构建金属/金属界面、金属/碳界面和金属间化合物(合金)等界面工程策略对电催化性能的调控.通过总结经典案例,重点强调了影响目标产物催化性能和选择性的关键因素和描述符.最后,针对目前电催化C-N偶联反应中存在的反应过程复杂、催化机理不明确、副反应严重、目标产物催化活性和选择性较低等挑战,对未来发展趋势提出了展望:(1)采用机器学习、分子模拟计算、密度泛函理论计算等预测并筛选高效的缺陷和界面工程的电催化剂,并对可能的活性位点和反应路径进行预测;(2)优化催化剂制备过程,实现催化剂中不同缺陷和界面的可控合成;(3)发展先进的原位表征技术监测电催化剂表面上的动态变化和识别反应过程中产生的中间体,结合理论计算对电催化C-N耦合反应的催化机理和反应路径进行深入地理解.综上所述,本文系统地总结了通过缺陷和界面工程调控催化剂结构并提高电催化C-N偶联反应合成含氮有机物的策略,并对该领域目前存在的挑战和未来的发展前景进行了展望,为促进电化学C-N偶联反应的工业化应用提供借鉴.

Comprehensive understanding of the thriving electrocatalytic nitrate/nitrite reduction to ammonia under ambient conditions

Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the conventional Haber–Bosch process that operates under harsh conditions,which consumes large quantities of fossil fuels and releases a large amount of carbon dioxide.As an alternative,electrosynthesis is a prospective method for producing NH_(3)under normal temperature and pressure conditions.Although electrocatalytic nitrogen reduction to ammonia has attracted considerable attentions,the low solubility of N_(2)and high N≡N cracking energy render the achievements of high NH_(3) yield rate and Faradaic efficiency difficult.Nitrate and nitrite(NO_(x)^(-))are common N-containing pollutants.Due to their high solubilities and low dissociation energy of N=O,NO_(x)^(-)−are ideal raw materials for NH_(3) production.Therefore,electrocatalytic NO_(x)^(-)−reduction to NH_(3)(eNO_(x)RR)is a prospective strategy to simultaneously realise environmental protection and NH_(3) synthesis.This review offers a comprehensive understanding of the thriving eNO_(x)RR under ambient conditions.At first,the popular theory and mechanism of eNO_(x)RR and a summary of the measurement system and evaluation criteria are introduced.Thereafter,various strategies for developing NO_(x)−reduction catalysts are systematically presented and discussed.Finally,the challenges and possible prospects of electrocatalytic NO_(x)^(-1) reduction are outlined to facilitate energy-saving and environmentally friendly large-scale synthesis of NH_(3) in the future.

Comprehensive understanding and rational regulation of microenvironment for gas-involving electrochemical reactions

Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance(activity,selectivity,and durability)remains unclear.Here,we provide a comprehensive understanding of the interfacial microenvironment of gas-involving electrocatalysis,including carbon dioxide reduction reaction and nitrogen reduction reaction,and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion,proton supply,and electron transfer.This categorization allows a systematic survey of the literature focusing on electrolyzer-level(optimization of the device,control of the experimental condition,and design of the working electrode),electrolytelevel(increase of gas solubility,regulation of proton supply,and substitution of anodic reaction),and electrocatalyst-level strategies(promotion of gas affinity,adjustment of hydrophobicity,and enhancement of conductivity),aiming to retrieve the correlations between the microenvironment and electrochemical performance.Finally,priorities for future studies are suggested to support the comprehensive improvement of next-generation gas-involving electrochemical reactions.

Deciphering engineering principle of three-phase interface for advanced gas-involved electrochemical reactions

As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen evolution reaction(HER),have become an emerging research direction and have gained increasing attention due to their advantages of environmental friendliness and sustainability.Various studies have been designed to accelerate sluggish kinetics but with limited results.Most of them promote the reaction by modulating the intrinsic properties of the catalyst,ignoring the synergistic effect of the reaction as a whole.Due to the introduction of gas,traditional liquid-solid two-phase reactions are no longer applicable to future research.Since gas-involved electrochemical reactions mostly occur at the junctions of gaseous reactants,liquid electrolytes and solid catalysts,the focus of future research on reaction kinetics should gradually shift to three-phase reaction interfaces.In this review,we briefly introduce the formation and constraints of the three-phase interface and propose three criteria to judge its merit,namely,the active site,mass diffusion and electron mass transfer.Subsequently,a series of modulation methods and relevant works are discussed in detail from the three improvement directions of‘exposing more active sites,promoting mass diffusion and accelerating electron transfer’.Definitively,we provide farsighted insights into the understanding and research of three-phase interfaces in the future and point out the possible development direction of future regulatory methods,hoping that this review can broaden the future applications of the three-phase interface,including but not limited to gas-involved electrochemical reactions.

Li^(+)-ion bound crown ether functionalization enables dual promotion of dynamics and thermodynamics for ambient ammonia synthesis

Electrosynthesis of ammonia from the reduction of nitrogen is still confronted with the limited supply of gas reactant in dynamics as well as high activation barrier in thermodynamics.Unfortunately,despite tremendous efforts devoted to electrocatalysts themselves,they still fail to tackle the above two challenges simultaneously.Herein,we employ a heterogeneous catalyst adlayer-composed of crown ethers associated with Li^(+)ions-to achieve the dual promotion of dynamics and thermodynamics for ambient ammonia synthesis.Dynamically,the bound Li^(+)ions interact with the strong quadrupole moment of nitrogen,and trigger considerable reactant flux toward the catalyst.Thermodynamically,Li^(+)associated with the oxygen of crown ether achieves a higher density of states at the Fermi level for the catalyst,enabling effortless electron transfer from the catalysts to nitrogen and thus greatly reducing the activation barrier.As expected,the proof-of-concept system achieves an ammonia yield rate of 168.5μg h^(-1)mg^(-1)and a Faradaic efficiency of 75.3%at-0.3 V vs.RHE.This system-level approach opens up pathways for tackling the two key challenges that have limited the field of ammonia synthesis.

Solid-Phase Enzymatic Peptide Synthesis to Produce an Antioxidant Dipeptide

Peptide bond synthesis is favorable to the production of bioactive small peptides. However, the abuse of toxic reagents remains an issue for chemical synthesis method, whereas the low product yield and purity limit the widespread use of enzymatic method. In this study, a new solid-phase enzymatic peptide synthesis(SPEPS) strategy was developed to produce an antioxidant tyrosine-alanine dipeptide(Tyr-Ala) by using recombinant carboxypeptidase Y(CPY) as the catalyst. The general SPEPS procedure involves three steps. First, the N-protected acyl donor was covalently attached to solid resin. Second,the peptide bond was condensed between the acyl donor and the nucleophile under the catalysis of CPY. Finally, one-step cleavage was performed to remove the protecting group and cleave the peptides from solid resin. Upon the optimization of reaction conditions, 77.92%(±2.723%) yield of Tyr-Ala with high product purity of 90.971%(±2.695%) was obtained.In addition, the antioxidant activity of Tyr-Ala was determined by ABTS method, indicating that the synthesized Tyr-Ala obtained by SPEPS showed a superior antioxidant capability compared with commercial glutathione.

Advanced In Situ Characterization Techniques for Direct Observation of Gas-Involved Electrochemical Reactions

Gas-involved electrochemical reactions provide feasible solutions to the worldwide energy crisis and environmental pollution.It has been recognized that various elements of the reaction system,including catalysts,intermediates,and products,will undergo real-time variations during the reaction process,which are of significant meaning to the in-depth understanding of reaction mechanisms,material structure,and active sites.As judicious tools for real-time monitoring of the changes in these complex elements,in situ techniques have been exposed to the spotlight in recent years.This review aims to highlight significant progress of various advanced in situ characterization techniques,such as in situ X-ray based technologies,in situ spectrum technologies,and in situ scanning probe technologies,that enhance our understanding of heterogeneous electrocatalytic carbon dioxide reduction reaction,nitrogen reduction reaction,and hydrogen evolution reaction.We provide a summary of recent advances in the development and applications of these in situ characterization techniques,from the working principle and detection modes to detailed applications in different reactions,along with key questions that need to be addressed.Finally,in view of the unique application and limitation of different in situ characterization techniques,we conclude by putting forward some insights and perspectives on the development direction and emerging combinations in the future.

Kinetically Controlled Carboxypeptidase-Catalyzed Synthesis of Novel Antioxidant Dipeptide Precursor BOC-Tyr-Ala

Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.

A facile strategy to construct MOF-based nanocatalyst with enhanced activity and selectivity in oxytetracycline degradation

Recently,many efforts have been dedicated to construct artificial catalysts with enzyme-like activity.However,it is still a big challenge to endow artificial catalysts with specific substrate selectivity.In this study,we developed a facile strategy to construct a MIL-53(Fe)-based nanocatalyst with designable selectivity in the degradation of oxytetracycline(OTC).Through the Fe–O–P conjunction,oxytetracycline aptamer(OA)can be easily anchored on MIL-53(Fe)to provide the specific site for OTC binding.We verified that the obtained MIL-53(Fe)-Apt nanocatalyst displayed enhanced catalytic ability in the degradation of OTC,whereas obvious suppression toward other substrate analogues.This performance therefore brings about an anticipated selectivity toward OTC.Moreover,we highlighted that the configuration of aptamers on MIL-53(Fe)can be modulated through varying conjunction mode.Structure–function analysis revealed that aptamer configuration affects the local concentration of substrate around catalytic site,which thus decides the catalytic performance toward OTC.This work presented a facile and promising strategy for developing artificial catalysts with designable selectivity.

钢轨表面三维疲劳裂纹扩展数值分析

在车轮循环滚动接触载荷作用下,钢轨接触表面裂纹问题频发,严重威胁高速列车运行安全,开展钢轨表面三维滚动接触疲劳裂纹扩展分析意义重大.首先,考虑不同初始裂纹角度,建立钢轨轨头含初始裂纹的三维有限元模型,对钢轨表面施加循环滚动接触载荷,进行轮轨滚动接触计算;然后,基于相互作用积分法计算裂纹前缘的应力强度因子;最后,采用最大周向应力准则和Paris公式计算当前状态下裂纹扩展方向和扩展速率,进而更新下一时刻的裂纹形状和尺寸.通过对上述过程重复实现,从而预测钢轨表面三维裂纹的扩展路径.加载过程中裂纹前缘应力强度因子计算结果表明,随着初始裂纹角度增加,K_(Ⅰ)的峰值逐渐减小,K_(Ⅱ)的峰值逐渐增大,裂纹前缘各位置的等效应力强度因子逐渐减小;裂纹前缘节点的位置越靠近钢轨表面,等效应力强度因子越大.疲劳裂纹扩展计算结果表明,随着循环次数的增加,不同初始角度下的裂纹都发生了偏折,逐渐朝着钢轨深度方向扩展,且裂纹的初始角度越大,发生扩展时需要的循环次数越多.对比三种初始裂纹角度下裂纹长度随循环次数的演化曲线可以发现,初始裂纹角度越小,裂纹扩展速率越大.所开发的方法也适用于研究钢轨多个裂纹的交互作用和其他位置的裂纹扩展问题,可为在役钢轨的剩余寿命提供技术支持.

高熵合金作为一种优异电催化剂的理解、合理设计和应用:综述

高熵合金近年来在电催化领域广受关注.由于其四大“核心效应”,即高熵效应、晶格畸变效应、迟滞扩散效应和鸡尾酒效应,高熵合金在诸多电催化反应中展现出了优异的活性和选择性.然而在已报道的文献综述中,有关其优异性能的理解以及合理设计的系统性总结仍然具有局限性.本文不仅综述了高熵合金电催化剂的特点和设计准则,还对其应用的最新进展进行了系统性的归纳整理,对高熵合金未来的发展具有指导意义.首先我们从多个角度阐明了高熵合金作为一种优异电催化剂的原因,包括其出色的机械性能、可优化的结构和组成、大量具有高本征活性的活性位点,以及出色的稳定性.为了进一步深入对高熵合金电催化剂的理解,我们还从设计准则、元素选择,以及理论计算预测材料性质等角度,详细介绍了高熵合金的合理设计.随后,我们介绍了高熵合金电催化剂在电解水、有机小分子氧化、燃料电池和碳/氮基转化反应的最新研究进展,其中还包括了一系列理论计算和原位表征在理解催化反应机理方面的应用.最后,我们展望了高熵合金电催化剂在未来发展中面临的挑战和机遇.

Biomineralization-inspired copper-cystine nanoleaves capable of laccase-like catalysis for the colorimetric detection of epinephrine

Recently,many efforts have been dedicated to creating enzyme-mimicking catalysts to replace natural enzymes in practical fields.Inspired by the pathological biomineralization behaviour of L-cystine,in this study,we constructed a laccase-like catalyst through the co-assembly of L-cystine with Cu ions.Structural analysis revealed that the formed catalytic Cu-cystine nanoleaves(Cu-Cys NLs)possess a Cu(I)-Cu(II)electron transfer system similar to that in natural laccase.Reaction kinetic studies demonstrated that the catalyst follows the typical Michaelis-Menten model.Compared with natural laccase,the Cu-Cys NLs exhibit superior stability during long-term incubation under extreme pH,high-temperature or high-salt conditions.Remarkably,the Cu-Cys NLs could be easily recovered and still maintained 76%of their activity after 8 cycles.Finally,this laccase mimic was employed to develop a colorimetric method for epinephrine detection,which achieved a wider linear range(9–455μmol·L^(−1))and lower limit of detection(2.7μmol·L^(−1)).The Cu-Cys NLs also displayed excellent specificity and sensitivity towards epinephrine in a test based on urine samples.

Eliminating nitrogen chemisorption barrier with single-atom supported yttrium cluster via electronic promoting effect for highly efficient ammonia synthesis

Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions,but promoting this process remains a significant challenge.Here,by loading yttrium clusters onto a single-atom support,an electronic promoting effect is triggered to successfully eliminate the nitrogen chemisorption barrier and achieve highly efficient ammonia synthesis.Density functional theory calculations reveal that yttrium clusters with abundant electron orbitals can provide considerable electrons and greatly promote electron backdonation to the N2 antibonding orbitals,making the chemisorption process exothermic.Moreover,according to the“hot atom”mechanism,the energy released during exothermic N2 chemisorption would benefit subsequent N2 cleavage and hydrogenation,thereby dramatically reducing the energy barrier of the overall process.As expected,the proof-of-concept catalyst achieves a prominent NH3 yield rate of 48.1μg·h^(−1)·mg^(−1)at−0.2 V versus the reversible hydrogen electrode,with a Faradaic efficiency of up to 69.7%.This strategy overcomes one of the most serious obstacles for electrochemical ammonia synthesis,and provides a promising method for the development of catalysts with high catalytic activity and selectivity.

Cystine-assisted accumulation of gold nanoparticles on ZnO to construct a sensitive surface-enhanced Raman spectroscopy substrate

Recently,various semiconductor/metal composites have been developed to fabricate surfaceenhanced Raman spectroscopy substrates.However,low metal loading on semiconductors is still a challenge.In this study,cystine was introduced to increase the accumulation of gold nanoparticles on zinc oxide,owing to the biomineralization_property of_cystine.Morphological analysis revealed that the obtained ZnO/Au/cystine composite not only had a higher metal loading but also formed a porous structure,which is beneficial for Raman performance.Compared with ZnO/Au,the ZnO/Au/cystine substrate displayed a 40-fold enhancement in the Raman signal and a lower limit of detection(10^(-11) mol·L^(-1))in the detection of rhodamine 6G.Moreover,the substrate has favorable homogeneity and stability.Finally,ZnO/Au/cystine displayed excellent performance toward crystal violet and methylene blue in a test based on river water samples.This study provided a promising method to fabricate sensitive semiconductor/noblemetal-based surface-enhanced Ramans spectroscopy substrates for Raman detection.

Asymmetric electrode design with built-in nitrogen transfer channel achieving maximized three-phase reaction region for electrochemical ammonia synthesis

Carbon-free electrochemical nitrogen reduction reaction(NRR)is an appealing strategy for green ammonia synthesis,but there is still a significant performance bottleneck.Conventional working electrode is usually flooded by the electrolyte during the NRR test,and only the surface material could get access to the nitrogen,which inevitably gives rise to sluggish reaction rate.Herein,an asymmetric electrode design is proposed to tackle this challenge.An aerophilic layer is constructed on one face of the electrocatalyst-loaded electrode,while the other side maintains its original structure,aiming to achieve facilitated nitrogen transfer and electrolyte permeation within the conductive skeleton simultaneously.This asymmetric architecture affords extensive threephase reaction region within the electrode as demonstrated by the combination of theoretical simulations and experimental measurements,which gives full play to the loaded electrocatalyst.As expected,the proofof-concept asymmetric electrode delivers an NH_(3)yield rate of 40.81μg h^(−1)mg^(−1)and a Faradaic efficiency of 71.71%at−0.3 V versus the reversible hydrogen electrode,which are more than 4 and 7 times that of conventional electrode,respectively.This work presents a versatile strategy for enhancing the interfacial reaction kinetics and is instructive to electrode design for gas-involved electrochemical reactions.