Modulating the coordination environment of active sites on catalyst surfaces is crucial to developing effective catalysts and controlling catalysis. However, this may be a highly challenging procedure. Guided by the first-principles calculations, the modification of the coordination environment of active sites on MoC nanoparticle surfaces is experimentally accomplished by anchoring pyridinic N atom rings of holey graphene on Mo atoms. The rings produce electrostatic forces that enable the tuning of the Mo sites′ affinity to reaction intermediates, which passivates Mo hollow sites, activates Mo top sites, and reduces the overadsorption of OH on the Mo active sites, as predicted by calculations. The atomic-level modification is well confirmed by atomic-resolution imaging, high-resolution electron tomography, synchrotron soft X-ray spectroscopy, and operando electrochemical infrared spectroscopy. Consequently, the Faradaic efficiency for CO2 reduction to CH4 is enhanced from 16% to 89%, a record high efficiency so far, in aqueous electrolytes. It also exhibits a negligible activity loss over 50 h.
|Journal||Advanced Energy Materials|
|Publication status||Published - 2021 Jun 24|
Bibliographical noteFunding Information:
L.L.H., X.J.L., and J.H. contributed equally to this work. The authors at TJUT acknowledge support from the National Key R&D Program of China (2017YFA0700104), the National Science Fund for Distinguished Young Scholars (51825102), the National Natural Science Foundation of China (51971157, 21601136, 51671145, and 51761165012), and the Tianjin Science Fund for Distinguished Young Scholars (19JCJQJC61800). The authors at the UCI acknowledge support from H.L.X.'s startup funding. This research used the resources of the Center for Functional Nanomaterials and the 23‐ID‐2 (IOS) beamline of the National Synchrotron Light Source II, two U.S. Department of Energy (DOE) Offices of Science User Facilities operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE‐SC0012704. The work carried out by R.R.A. and Z.L. at Brookhaven National Laboratory was supported by the Division of Chemical Sciences, Geosciences, & Biosciences, Office of Basic Energy Sciences and under Contract No. DE‐SC0012704 with the U.S. Department of Energy.
© 2021 Wiley-VCH GmbH
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)