摘要：Efficient tandem reactions on a single catalytic nanostructure would be beneficial to improving chemical transformation efficiency and reducing safety implications. It is imperative to identify the active sites for each single step reaction so that the entire reaction process can be optimized by designing and integrating the sites. Herein, hydrogen transfer reaction is taken as a proof-of-concept demonstration to show that the spatial integration of active sites is important to the catalytic efficiency of the entire process in tandem reactions. We identified specific active sites (i.e., various sites at faces versus corners and edges) for formic acid decomposition and alkene/nitrobenzene hydrogenation-the two steps in hydrogen transfer reactions, by employing three different shapes of Pd nanocrystals in tunable sizes. The investigation reveals that the decomposition of formic acid occurs preferentially at the edge sites of cubic nanocrystal and the plane sites of octahedral/ tetrahedral nanocrystals, while the hydrogenation takes place mainly at the edge sites of both cubic and octahedral/ tetrahedral nanocrystals. The consistency of active edge sites during different step reactions enables cubic nanocrystals to exhibit a higher activity than octahedral nanocrystals in hydrogen transfer reactions, although octahedrons offer comparable activities to cubes in formic acid decomposition and hydrogenation reactions. Guided by these findings, we further improved the overall performance of tandem catalysis by specifically promoting the limiting step through nanocatalyst design. This work provides insights into the rational design of heterogeneous nanocatalysts in tandem reactions.

摘要：Transition metal Ni anchored in carbon material represents outstanding 2e?oxygen reduction reaction(ORR)catalytic selectivity,but enhancing the adsorption strength of intermediate*OOH to promote its selectivity remains a major ***,the NiX/Ni@NCHS composite catalyst with heteroatom doping(O,S)is modulated by controlling partial pyrolysis strategies on honeycomb-like porous carbon to manipulate the electronic structure of the metal *** the synergistic effect of honeycomb structure and O atom,NiO/Ni@NCHS-700 exhibits an exceptional H_(2)O_(2)selectivity of above 89.1%across a wide potential range from 0.1 to 0.6 V in an alkaline electrolyte,and an unexpected H_(2)O_(2)production rate up to 1.47 mol gcat^(-1) h^(-1)@0.2 V,which outperforms most of the state-of-the-art ***,NiS/Ni@NCHS exhibits excellent electrocatalytic performance,with 2e?ORR selectivity of 91.3%,H_(2)O_(2)yield of 1.85@0.3 *** functional theory simulations and experiments results reveal that the heteroatom doping(O,S)method has been employed to regulate the adsorption strength of Ni atoms with*OOH,and combined with the self-sacrificing template-assisted pyrolysis approach to improve the microstructure of catalysts and optimize the active *** heteroatom doping method in this work provides significant guidance for promoting 2e?ORR electrocatalysis to produce H_(2)O_(2).