摘要：The fixation and conversion of CO_(2)frommedium-and high-temperature industrial exhaust gases arescientifically important and challenging tasks owing to theharsh conditions ***_(2)O_(3),a stable p-block compound,is surprisingly active in the thermal conversion of hot CO_(2)waste gas,but its underlying mechanism remains *** study,we investigated CO_(2)adsorption and activationacross 11 different Ga_(2)O_(3)-terminated faces using densityfunctional *** transfer and chemical bond analysesrevealed the occurrence of two distinct activation mechanismsinvolving synchronous electron gain and loss,driven by astrong synergetic effect between Ga cations and O anions onthe substrate *** Ga-O synergy enhances the CO_(2)activation efficiency compared with single active sites,with CO_(2)^(δ+) cation more readily capturing H atom than CO_(2)^(δ–).Tothe best of our knowledge,such a dual activation mechanismhas not been reported before,particularly for p-block *** findings provide new insights into the direct catalyticconversion of CO_(2)emissions and offer strategies for the rational design of industrial-grade catalysts for medium-andhigh-temperature CO_(2)tail gas conversion.

摘要：We report in situ doping of brushite on zinc manganese oxide（ZMO）, fabricated by calcining a Mn（II） oxalate‐impregnated metal‐organic framework. The doping process was conducted in com‐bination with the photocatalytic water oxidation reaction which was catalyzed by ZMO in neutral phosphate‐buffered aqueous solution containing [Ru（bpy）3]^2＋‐Na2S2O8 and calcium（II） triflate salt, exhibiting greatly enhanced water oxidation performance with optimized turnover frequency of 0.18 mmol（O2） mol（Mn）^（–1） s^（–1）. Different analytical techniques indicated that photodeposited calci‐um‐phosphate（CaP） acted as a co‐catalyst to promote the O2 evolution activity of ZMO. This system involved the use of manganese oxide and calcium ion, and the operation was conducted under am‐bient temperature and neutral conditions, thus, it efficiently mimicked the oxygen‐evolving complex in photosystem II.

摘要：光催化CO_(2)还原合成太阳能燃料对缓解CO_(2)排放引起的全球变暖和降低化石燃料消耗具有重要意义.然而,目前的光催化剂仍然存在反应动力学缓慢和选择性不理想的问题,特别是对于C_(2+)产物的生成,极大地限制了光催化的工业化进程.过去几十年中,关于太阳能驱动的CO_(2)还原的研究展示出鼓舞人心的结果,包括活性位点的构建.本综述重点介绍了通过构建活性位点制备原子级分散催化剂在光催化CO_(2)还原中的最新进展,包括两个独立的活性位点、成对双活性位点和基于活性位点构型的纳米团簇.此外,详细讨论了CO_(2)在活性位点上的活化机制和表征方法.特别是考虑到实验研究与实际应用之间的差距,整合实验和理论的结果,以实现潜在的结构-活性关系和高目标产物选择性发展.最后,概述了该领域存在的挑战,并展望了活性位点的合理设计和机理研究.

摘要：Defect engineering has become a promising approach to improve the performance of hydrogen evolution reaction(HER)***-noble transition metal-based catalysts(TMCs)have shown significant promise as effective alternatives to traditional platinum-group catalysts,attracting considerable ***,the industrial application of TMCs in electrocatalytic hydrogen production necessitates further optimization to boost both catalytic activity and *** review comprehensively examines the types,fabrication methods,and characterization techniques of various defects that enhance catalytic HER *** advancements include optimizing defect concentration and distribution,coupling heteroatoms with vacancies,and leveraging the synergy between bond lengths and ***-depth discussions highlight the electronic structure and catalytic mechanisms elucidated through in-situ characterization and density functional theory ***,future directions are identified,exploring novel defect types,emphasizing precision synthesis methods,industrial-scale preparation techniques,and strategies to enhance structural stability and understanding the in-depth catalytic *** review aims to inspire further research and development in defect-engineered HER catalysts,providing pathways for high efficiency and cost-effectiveness in hydrogen production.

摘要：Solar‐to‐chemical energy conversion is perceived as one of the most potential solutions to the current energy and environmental crisis,yet requires major scientific endeavors on the development of efficient and sustainable *** the composition and morphology of a semiconductor jointly for the purpose of improving photocatalysis efficiency remains ***,we rationally fabricated Cu‐doped ZnS nanoframes via a simple conjunct strategy of substitutional doping,chemical acidic etching,and sulfidation,aiming at enhancing the light utilization and charge separation/transfer efficiency for solar‐light‐driven hydrogen ***‐doped zeolitic imidazolate framework‐8(ZIF‐8)rhombic dodecahedrons are transformed to hollow Cu‐ZIF‐8 nanoframes converted to Cu‐ZnS nanoframes with three‐dimensional photocatalytic active surfaces via anisotropic chemical etching,which is further converted to Cu‐ZnS *** combining the merits of optimal heteroatom doping and frame‐like open architecture,the obtained 1%Cu‐doped ZnS nanoframe exhibits high photocatalytic activity under solar light irradiation with improved hydrogen production rate up to 8.30 mmol h^(–1) g^(–1) and excellent stability in the absence of cocatalysts,which is significantly improved in comparison with those of the bare ZnS and Cu‐ZnS with different *** work inspired by merging the merits of metal doping and anisotropic chemical etching may shed light on the rational design and fabrication of advanced photocatalysts.

摘要：The development of efficient and cost‐effective metal‐free electrocatalysts for oxygen reduction reaction(ORR)has become crucial for electrochemical energy ***,reasonably validating and precisely regulating the active sites for designing optimized materials are still ***,we report a precise and controllable tandem strategy to boost the ORR activity based on metal‐free covalent organic frameworks(MFCOFs)comprising imine‐N,thiophene‐S,or triazine‐*** these MFCOFs,post‐tandem BTT‐TAT‐COF structure displayed a more positive catalytic capability and excellent electrochemical stability,indicating that the synergistic catalysis of multiple active sites induced the ORR catalytic activity through the conjugated skeleton of the ***‐functional theory calculations suggest that the series‐connected backbone contained highly effective electrocatalytic active centers and provided synergistic *** importantly,this strategy highlights new opportunities for the advancement of efficient COF‐based metal‐free ORR catalysts.

摘要：This review summarizes a variety of experimentally identified gas‐phase catalytic cycles,all of which are mediated by atomic metal ions,bare metal clusters,metal oxide clusters or metal *** is placed on the latest advances in the unique catalytic reactivity of cluster‐confined single noble metal *** cycles discussed in this paper cover a wide range of inorganic and organic *** use of start‐of‐the‐art mass spectrometric instrumentation in conjunction with quantum chemistry calculations is also reported,as these techniques have determined the mechanistic details of the elementary steps of such catalytic *** important role of gas‐phase data in guiding the rational design of better‐performing catalysts in related condensed phase reactions is also *** particular,this review focuses on the following three topics:(1)the catalytic oxidation of carbon monoxide,(2)the catalytic functionalization of methane,and(3)catalytic decarboxylation.

摘要：The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild *** deduced that formation of an active zinc‐hydrogen(Zn‐H)species promoted hydride transfer from the hydrosilane to *** cooperative activation of the Lewis acidic ZnPc by strongly polar DMF,led to formation of activated amines and hydrosilanes,which promoted the chemical reduction of ***,the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity,representing a simple and sustainable pathway for the reductive transformation of CO2into valuable chemicals as an alternative to conventional halogen‐containing process.

摘要：Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) *** tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal *** pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt *** approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their ***,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced *** resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),*** S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density ***,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and **** study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.

摘要：越来越多的研究将有机电化学晶体管(OECT)用于新颖的电学设备,然而这些设备天然需要两个仪器电源,不利于将其应用于对能源供应有严格要求的便携和可穿戴体系.本文通过将单晶硅太阳能电池组装到OECT的回路中并以光作为燃料,构建了自供能和光调控功能的有机光电化学晶体管(OPECT)光电子器件.以基于聚(3,4-乙烯二氧噻吩)-聚(苯乙烯磺酸酯)(PEDOT:PSS)的耗尽型和增强型OECT为例,我们设计了不同的光寻址结构并系统地研究和比较了相应的特性.通过合适的光调制,我们实现了不同的器件行为,且这些器件表现出优异的性能.在应用层面,我们设计了光逻辑电路,其不同的特性可以通过相应的辐照度来调控;此外,我们展示了光控的OECT单极逆变器,并根据系统的能源供应和阻抗进行了优化.本工作代表着新型的OPECT光电子器件,合理地将其与柔性基底和太阳能电池组装有望应用于便携和可穿戴器件领域.