摘要：Understanding the influence of HCl on the NH_(3)-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification *** formation of chlorate species on the surface of the synthesized SbCeO_(x)catalyst,induced by HCl,significantly enhances low-temperature activity,as evidenced by a 30%increase in NO conversion at 155℃.Furthermore,it improves N_(2)selectivity at high temperatures,with a notable 17%increase observed at 405℃.Both experimental results and density functional theory calculations confirm that chlorate species form at Ce *** formation facilitates the creation of oxygen vacancies,boosting the oxygen exchange *** also increases NH_(3)adsorption at the Ce sites,promotes the formation of Sb-OH,and reduces competitive OH adsorption on these ***,compared with the reaction mechanism without HCl,the presence of chlorate species enhances NH_(3)adsorption and activation,which is vital for subsequent catalytic reactions.

摘要：Untreated urea-rich wastewater exerts severeadverse impacts on both the environment and human health,prompting extensive attention towards the urea oxidationreaction (UOR) as a sustainable technology to generate cleanenergy in recent years. UOR has a thermodynamic advantageover oxygen evolution reaction (OER) (1.23 V vs reversiblehydrogen electrode, RHE) and only requires 0.37 V (vs RHE),which is considered as an effective alternative to H_(2) production by water electrolysis. However, the inevitable kineticslowness and complex adsorption/desorption during the processhinder its practical application. Most traditional catalystsutilized for the UOR are comprised of precious metals, resulting in limited economic viability. Inspired by natural ureases, Ni-based catalysts have emerged as promisingalternatives owing to their rich deposits, low cost, and theregulated d orbitals of transition metal Ni, demonstratingconsiderable potential for UOR. Currently, numerous studieshave explored Ni-based hydroxides, oxides, chalcogenides, andphosphides in alkaline solutions. In this review, we will explorethe UOR reaction mechanism and summarize the catalystdesign strategies of various Ni-based catalysts recently, especially Ni-MOF, which has been rarely discussed before. Then,the broad prospects of UOR in practical applications aresummarized. Finally, based on the design strategies and performance comparisons discussed above, the challenges andprospects facing the future development of Ni-based electrocatalysts for the UOR will be presented.

摘要：许多具有d^(6)和d^(8)电子构型的第二和第三周期过渡金属配合物具有长寿命的金属中心到配体的电荷转移(MLCT)激发态,表现出优异的光化学和光物理性能。然而,这类金属普遍昂贵且在地壳中的丰度很低。因此,开发新型廉价和丰产第一周期过渡金属光功能配合物具有重要的理论研究意义和实际应用价值。其中,具有3d^(6)电子构型的Fe(Ⅱ)和3d^(5)电子构型的Fe(Ⅲ)光功能配合物引起了众多关注。其主要挑战为通过有效的配体设计调控Fe(Ⅱ)配合物的MLCT激发态,以及实现Fe(Ⅲ)配合物配体到金属的电荷转移(LMCT)激发态发光。近年来,相关研究取得了突破性的进展,具有较长MLCT激发态寿命的Fe(Ⅱ)配合物和LMCT发光的Fe(Ⅲ)配合物被陆续开发出来,并成功应用于光化学领域。在此,我们从配合物和配体设计出发,总结了Fe(Ⅱ)和Fe(Ⅲ)配合物激发态调控的最新进展。此外,我们还讨论了Fe(Ⅱ)/Fe(Ⅲ)配合物在光化学领域的潜在应用。

摘要：Designing Fischer-Tropsch synthesis(FTS)catalysts to selectively produce liquid hydrocarbon fuels is a crucial ***,we selectively introduced Co nanoparticles(NPs)into the micropores and mesopores of an ordered mesoporous MFI zeolite(OMMZ)through impregnation,which controlled the carbon number distribution in the FTS products by tuning the position of catalytic active sites in differently sized *** Co precursors coordinated by acetate with a size of 9.4×4.2×2.5Åand by 2,2‘-bipyridine with a size of 9.5×8.7×7.9Å,smaller and larger than the micropores(ca.5.5Å)of MFI,made the Co species incorporated in OMMZ's micropores and mesopores,*** carbon number products synthesized with the Co NPs confined in mesopores were larger than that in *** high jet and diesel selectivities of 66.5%and 65.3%were achieved with Co NPs confined in micropores and mesopores of less acidic Na-type OMMZ,*** and jet selectivities of 76.7%and 70.8%were achieved with Co NPs confined in micropores and mesopores of H-type OMMZ with Brönsted acid sites,respectively.A series of characterizations revealed that the selective production of diesel and jet fuels was due to the C-C cleavage suppressing of heavier hydrocarbons by the Co NPs located in mesopores.

摘要：Electrochemical nitrate(NO_(3)^(-))reduction offers a promising route for ammonia(NH_(3))synthesis from industrial wastewater using renewable ***,achieving selective and active NO_(3)^(-)to NH_(3)conversion at low potentials remains challenging due to complex multi-electron transfer processes and competing ***,we tackle this challenge by developing a cascade catalysis approach using synergistic active sites at Cu-Fe_(2)O_(3)interfaces,significantly reducing the NO_(3)^(-)to NH_(3)at a low onset potential to about+0.4 V_(RHE).Specifically,Cu optimizes^(*)NO_(3)adsorption,facilitating NO_(3)^(-)to nitrite(NO_(2)-)conversion,while adjacent Fe species in Fe_(2)O_(3)promote the subsequent NO_(2)-reduction to NH_(3)with favorable^(*)NO_(2)*** operating experiments,in situ Raman spectroscopy,and in situ infrared spectroscopy consolidate this improved onset potential and reduction kinetics via cascade *** NH_(3)partial current density of~423 mA cm^(-2)and an NH_(3)Faradaic efficiency(FENH_(3))of 99.4%were achieved at-0.6 V_(RHE),with a maximum NH_(3)production rate of 2.71 mmol h^(-1)cm^(-2)at-0.8 V_(RHE).Remarkably,the half-cell energy efficiency exceeded 35%at-0.27 V_(RHE)(80%iR corrected),maintaining an FENH_(3)above 90%across a wide range of NO_(3)^(-)concentrations(0.05^(-1)mol L^(-1)).Using 15N isotopic tracing,we confirmed NO_(3)^(-)as the sole nitrogen source and attained a 98%NO_(3)^(-)removal *** catalyst exhibit stability over 106-h of continuous operation without noticeable *** work highlights distinctive active sites in Cu-Fe_(2)O_(3)for promoting the cascade NO_(3)^(-)to NO_(2)^(-)and NO_(2)^(-)to NH_(3)electrolysis at industrial relevant current densities.

摘要：CO_(2)hydrogenation to value-added light olefins(C_(2-4)=)is crucial for the utilization and cycling of global carbon *** CO_(2)activation and carbon chain growth ability are key factors for iron-based catalysts for efficient CO_(2)conversion to target C_(2-4)=*** electronic interaction and confinement effect of electron-deficient graphene inner surface on the active phase are effective to improve surface chemical properties and enhance the catalytic ***,we report a core-shell FeCo alloy catalyst with graphene layers confinement prepared by a simple sol-gel *** electron transfer from Fe species to curved graphene inner surface modifies the surface electronic structure of the active phaseχ-(Fe_(x)Co_(1-x))_(5)C_(2)and improves CO_(2)adsorption capacity,enhancing the efficient conversion of CO_(2)and moderate C-C ***,the catalyst FeCoK@C exhibits C_(2-4)=selectivity of 33.0%while maintaining high CO_(2)conversion of 52.0%.The high stability without obvious deactivation for over 100 h and unprecedented C_(2-4)=space time yield(STY)up to 52.9 mmolCO_(2)·g^(-1)·h^(-1)demonstrate its potential for practical *** work provides an efficient strategy for the development of high-performance CO_(2)hydrogenation catalysts.

摘要：生物乙醇是重要的生物质平台分子,全球年产能约9000万吨,且乙醇分子化学键丰富,是化学键构成最具代表性的最小的含氧化合物分子,为其高值化转化提供了丰富的反应路径,近年来,引起科学界的广泛关注.本文对乙醇经O-H键定点活化、α-C-H键定点活化,O-H键/α-C-H键同时活化制备高附加值化学品的催化剂设计进行了介绍;对乙醇催化转化在催化剂理性设计、催化剂机理研究以及未来规模化放大等方面进行了展望.

摘要：It is a challenging task to efficiently convert deleterious hydrogen sulfide(H_(2)S)into less harmful products such as SO_(4)^(2-)*** an effort to address such issue,a step-scheme(S-scheme)heterojunction photocatalyst has been built by concatenating TiO_(2)(P25)and ultrathin Bi_(4)O_(5)Br_(2)into TiO_(2)/Bi_(4)O_(5)Br_(2)(namely,x-TB-y:x and y denote the molar ratio of TiO_(2):Bi_(4)O_(5)Br_(2)and pH value for solution-based synthesis,respectively)via in-situ hydrothermal *** S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge ***,the optimized heterojunction photocatalyst,i.e.,5-TB-9,showcases significantly high(>99%)removal efficiency against 10 ppm H_(2)S in a 17 L chamber within 12 minutes(removal kinetic rate r:0.7 mmol·h^(-1)·g^(-1),specific clean air delivery rate SCADR:5554 L·h^(-1)·g^(-1),quantum yield QY:3.24 E-3 molecules·photon^(-1),and space-time yield STY:3.24 E-3 molecules·photon^(-1)·mg^(-1)).Combined analysis of in-situ diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H_(2)S(i.e.,into SO_(4)^(2-)without forming any intermediate species).This work demonstrates the promising remediation potential of an S-scheme TiO_(2)/Bi_(4)O_(5)Br_(2)photocatalyst against hazardous H_(2)S gas for sustainable environmental remediation.

摘要：Metal-organic framework(MOF)nanostructures have emerged as a prominent class of materials in the advancement of electrochemical *** rational design of bimetallic MOF-functionalized microelectrode is of importance for improv-ing the electrochemical performance but still in great *** this work,the bimetallic FeCo-MOF nanostructures were assembled onto a gold disk ultramicroelectrode(Au UME,5.2μm in diameter)via an in-situ electrodeposition method,which enhanced the sensitive detection of epinephrine(EP).The in-situ electrodeposited FeCo-MOF exhibited a character-istic nanoflower-like morphology and was uniformly dispersed on the Au *** FeCo-MOF/Au UME demonstrated excellent electrochemical performance on the detection of EP with a high sensitivity of 36.93μA·μmol^(-1)·L·cm^(-2)and a low detection limit of 1.28μmol·L^(-1).It can be attributed to the nonlinear diffusion of EP onto the ultra-micro working substrate,coupled with synergistical catalytic activity of the bimetallic Fe,Co within MOF ***,the FeCo-MOF/Au UME has been successful applied to the analysis of EP in human serum samples,yielding high recovery *** results not only contribute to the expansion of the research area of electrochemical sensors,but also provide novel insights and directions into the development of high-performance MOF-based electrochemical sensors.

摘要：Covalent organic frameworks(COFs)are garnering significant interest in photocatalytic CO_(2) ***,their limited efficiency in separating photogenerated carriers and the scarcity of catalytic sites lead to suboptimal photocatalytic *** we develop a molecular engineering approach to design a pyrene-based COF(PyTa-H COF)confined cobalt single atoms photocatalyst(Co SACs)for CO_(2) *** moiety is introduced to enhance visible-light harvesting capability and improve charge separation in the ***,Co SACs enhance the photocatalytic activity by accelerating the migration of photo-induced carriers and reducing the reaction energy of the rate-determining ***,PyTa-H@Co achieves a CO production rate of 18.36 mmol g^(−1) h^(−1) and a selectivity of 94%in 4 h under visible light irradiation,which is comparable to the reported best-performing *** functional theory calculations reveal that the Co SACs greatly stabilize*COOH and significantly reduce the energy of the decisive step,leading to outstanding photocatalytic *** work,through molecular engineering design,highlights the critical relationship between catalyst structure and function in enhancing photocatalytic efficiency.