Atomically Dispersed CuNx Sites from Thermal Activation of Boron Imidazolate Cages for Electrocatalytic Methane Generation
Soumyodip Banerjee, Justin Gorham, Maxime Siegler, Natalia Drichko, Joshua Wright, Nicholas Bedford, Sara Thoi
Atomically dispersed heteroatom coordinated metal sites (ADMS) have been recognized as promising candidates for electrochemical conversion. Among a diverse range of molecular precursors for ADMS synthesis, framework materials are particularly interesting due to the presence of pre-formed heteroatom coordinated molecular active sites. Herein, we demonstrate that the copper boron imidazolate cage, BIF-29(Cu) can be an ideal precursor for nitrogen coordinated single site Cu catalyst for electrocatalytic carbon dioxide reduction (CO2RR). Although the pristine material exhibited moderate methane selectivity over hydrogen evolution reaction (HER), the catalytic performance is significantly enhanced (2x enhancement, 55 % CH4 at -1.25 V vs RHE) by mild thermal activation. Our extensive spectroscopic characterizations indicate the transformation of crystalline BIF-29(Cu) into an amorphous carbonaceous material comprising isolated CuN2 sites. This work encourages the discovery of single-site electrocatalytic systems through a rational selection of molecular precursor and calcination parameters for desired electrocatalytic selectivity.
, Gorham, J.
, Siegler, M.
, Drichko, N.
, Wright, J.
, Bedford, N.
and Thoi, S.
Atomically Dispersed CuNx Sites from Thermal Activation of Boron Imidazolate Cages for Electrocatalytic Methane Generation, ACS Applied Energy Materials, [online], https://doi.org/10.1021/acsaem.2c01174, https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=933004
(Accessed September 24, 2023)