镍基金属有机框架及其衍生物在电催化析氧反应中的研究进展

作为未来最有潜力的制氢技术之一,电解水为解决环境污染和能源危机等问题提供了一种有效的解决途径。然而,阳极析氧反应缓慢的动力学和较高的过电位使其成为电解水装置效率提升的主要瓶颈。因此,开发高活性和高稳定性的析氧反应催化剂对于电解水技术的发展具有重要意义。近年来,镍基金属有机框架材料因其具有丰富可调的拓扑结构、较大的比表面积以及多孔特性,在催化领域受到了越来越多的关注。本文综述了镍基金属有机框架及其衍生材料在析氧催化研究中的最新进展。首先简要介绍了镍基材料在析氧反应中的原理及评价析氧催化剂活性的一些重要参数,并列举了几种镍基金属有机框架材料的结构及其在催化中的优势。随后,结合近年来发表的文献,对单金属、双金属和三金属镍基金属有机框架材料及其衍生物在析氧催化中的研究进展进行了总结与讨论,重点分析了该类材料的设计策略和催化机理。最后对该领域目前所面临的主要挑战以及未来的发展趋势进行了总结与展望。

Antimony oxides-protected ultrathin Ir-Sb nanowires as bifunctional hydrogen electrocatalysts

Developing electrocatalysts with fast kinetics and long-term stability for alkaline hydrogen oxidation reaction(HOR)and hydrogen evolution reaction(HER)is of considerable importance for the industrial production of green and sustainable energy.Here,an ultrathin Ir-Sb nanowires(Ir-Sb NWs)protected by antimony oxides(SbO_(x))was synthesized as an efficient bifunctional catalyst for both HOR and HER under alkaline media.Except from the much higher mass activities of Ir-Sb nanowires than those of Ir nanowires(Ir NWs)and commercial Pt/C,the SbO_(x) protective layer also contributes to the maintenance of morphology and anti-CO poisoning ability,leading to the long-term cycling performance in the presence of CO.Specifically,the Ir-Sb NW/SbO_(x) exhibits the highest catalytic activities,which are about 3.5 and 4.8 times to those of Ir NW/C and commercial Pt/C toward HOR,respectively.This work provides that the ultrathin morphology and H_(2)O-occupied Sb sites can exert the intrinsic high activity of Ir and effectively optimize the absorption of OH*both in alkaline HER/HOR electrolysis.

Identification and characterization of camptothecin tailoring enzymes in Nothapodytes tomentosa

Camptothecin is a complex monoterpenoid indole alkaloid with remarkable antitumor activity.Given that two C-10 modified camptothecin derivatives,topotecan and irinotecan,have been approved as potent anticancer agents,there is a critical need for methods to access other aromatic ringfunctionalized congeners(e.g.,C-9,C-10,etc.).However,contemporary methods for chemical oxidation are generally harsh and low-yielding when applied to the camptothecin scaffold,thereby limiting the development of modified derivatives.Reported herein,we have identified four tailoring enzymes responsible for C-9 modifications of camptothecin from Nothapodytes tomentosa,via metabolomic and transcriptomic analysis.These consist of a cytochrome P450(Nt CPT9H)which catalyzes the regioselective oxidation of camptothecin to 9-hydroxycamptothecin,as well as two methyltransferases(Nt OMT1/2,converting 9-hydroxycamptothecin to 9-methoxycamptothecin),and a uridine diphosphate-glycosyltransferase(Nt UGT5,decorating 9-hydroxycamptothecin to9-β-D-glucosyloxycamptothecin).Importantly,the critical residues that contribute to the specific catalytic activity of Nt CPT9H have been elucidated through molecular docking and mutagenesis experiments.This work provides a genetic basis for producing camptothecin derivatives through metabolic engineering.This will hasten the discovery of novel C-9 modified camptothecin derivatives,with profound implications for pharmaceutical manufacture.

Defect engineered 2D mesoporous Mo-Co-O nanosheets with crystalline-amorphous composite structure for efficient oxygen evolution

Two-dimensional(2D)mesoporous metal-oxide(hydroxide)nanomaterials with defects are promising towards the realization of efficient electrocatalysis.Herein,we report a facile and effective one-pot solvothermal route to synthesize mesoporous Mo_(x)-Co-O hybrid nanosheets(NSs)which is composed of crystalline Mo_(4)O_(11) and amorphous cobalt hydroxide.Due to the corrosion of 1-octylamine at high temperatures,abundant mesoporous holes are created in situ over the Mo_(x)-Co-O hybrid NSs during the solvothermal process,which is beneficial to increasing the electrochemical surface area.The dimension of the Mox-Co-O NSs,size of mesoporous and the concentration of defects can be easily modulated by controlling the molar ratio of Mo/Co.Electrochemical measurements reveal that the 2D mesoporous Mo_(x)-Co-O NSs show an excellent activity for the oxygen evolution reaction with the highest catalytic activity of η_(10)=276 mV at 10 mA cm^(−2)in 1 mol L^(−1)KOH.Enhanced adsorption of intermediates and abundant oxygen vacancies achieved by appropriate Mo doping are the two main factors that contribute to the excellent catalytic activity of Mo_(0.2)-Co-O NSs.This work,with the construction of 2D metal-oxide(hydroxide)crystallineamorphous nanomaterials possessing abundant holes,oxygen vacancies and enhanced adsorption of intermediates,provides important insight on the design of more efficient catalysts.

Single-Site Cu-Doped PdSn Wavy Nanowires for Highly Active,Stable,and CO-Tolerant Ethanol Oxidation Electrocatalysis

Developing a catalyst to break the tradeoff relation-ship between the catalytic activity and antipoisoning property toward the ethanol oxidation reaction(EOR)is of critical importance to the development of direct ethanol fuel cells(DEFCs),but remains challenging.Here,we developed a unique class of single-site Cu-doped PdSn wavy nanowires(denoted as SS Cu−PdSn WNWs)with promoted activity and durability toward alkaline EOR.Detailed characterizations reveal the atomic isolation of Cu species dispersed on the surface of the PdSn WNWs with distinct wavy structure and grain boundaries.The created SS Cu−PdSn WNWs exhibit an enhanced EOR performance in terms of mass activity,which is higher than those of PdSn WNWs,commercial Pd black,and commercial Pd/C,respectively.Moreover,the SS Cu−PdSn WNWs can also show improved stability as compared to other catalysts due to the improved antipoisoning property from the unique surface anchoring structure.Further investigations demonstrate that the doped SS Cu can strongly inhibit the adsorption of CO and promote the reaction process of EOR.DFT results reveal that the doped Cu shifts down the d-band center of PdSn,thereby modifying the adsorption of intermediates and reducing the reaction barrier of EOR.This work maps a pathway for optimally boosting EOR performance with surface engineering via atomic doping.