通过调控金属-载体界面间的电子传递提高催化性能已被证明是一种有效且具有挑战性的催化研究策略。本文提出了一种调变铂/碳纳米复合物催化剂中碳载体表面化学性质（载体表面吸电子/给电子含氧官能团），用以精细调控负载金属铂电子性质及其催化性能的方法。本文以氨硼烷水解制氢作为模型反应，结合密度泛函理论（DFT）计算、先进表征技术、动力学及同位素研究，定量关联了载体表面化学性质、铂电荷数与电子结合能、活化熵与活化焓，以及催化活性之间的关系。通过解耦碳载体表面复杂的影响因素，提出铂电荷数可作为实验易测量的催化活性描述符，其中通过铂电荷数的调变可使催化性能提升15倍。在此基础上，首次建立了包含催化剂活性描述符与活性位数量的介观动力学模型，可分别定量催化剂电子与几何效应，并预测催化性能的变化。本文提出的介观动力学模型可进一步用于设计与构筑高效的金属/碳催化剂。

Taming the electron transfer across metal–support interfaces appears to be an attractive yet challenging methodology to boost catalytic properties. Herein, we demonstrate a precise engineering strategy for the carbon surface chemistry of Pt/C catalysts—that is, for the electron-withdrawing/donating oxygen-containing groups on the carbon surface—to fine-tune the electrons of the supported metal nanoparticles. Taking the ammonia borane hydrolysis as an example, a combination of density functional theory (DFT) calculations, advanced characterizations, and kinetics and isotopic analyses reveals quantifiable relationships among the carbon surface chemistry, Pt charge state and binding energy, activation entropy/enthalpy, and resultant catalytic activity. After decoupling the influences of other factors, the Pt charge is unprecedentedly identified as an experimentally measurable descriptor of the Pt active site, contributing to a 15-fold increment in the hydrogen generation rate. Further incorporating the Pt charge with the number of Pt active sites, a mesokinetics model is proposed for the first time that can individually quantify the contributions of the electronic and geometric properties to precisely predict the catalytic performance. Our results demonstrate a potentially groundbreaking methodology to design and manipulate metal–carbon catalysts with desirable properties.