Theoretical understanding of electrocatalysis beyond thermodynamic analysis

As the green and sustainable development of human society highly relies on renewable energy, it has been recognized that electrocatalysis is a key technology to this end. High efficient ways of carbon-neutralization (eCO2RR), reverse artificial nitrogen cycle (RANC), and oxygen chemistry (OER and ORR) all can be driven by electrocatalysis. Advanced theoretical study is an important means to fundamentally understanding electrocatalytic reactions. Herein, we review a few significant issues in theoretical electrocatalysis. First, electrochemical barriers and potential effects are essential for a more accurate description of reaction mechanism and activity. Meanwhile, consideration of competitive reaction path is also one of the important aspects, as novel insights and anomalous volcano trend can be obtained. Finally, a microenvironment exerted by confined space can tune the capacitance of electrochemical interface and (electro)chemical potential of proton, resulting in a possibility to improve reaction activity, which opens a new avenue for design of catalyst.