Linkage Effect in the Heterogenization of Cobalt Complexes by Doped Graphene for Electrocatalytic CO₂ Reduction

Abstract

Immobilization of planar Co II -2,3-naphthalocyanine (NapCo) complexes onto doped graphene resulted in ah eterogeneous molecular Co electrocatalyst that was active and selective to reduce CO 2 into CO in aqueous solution. A systematic study revealed that graphitic sulfoxide and carboxyl dopants of graphene were the efficient binding sites for the immobilization of NapCo through axial coordination and resulted in active Co sites for CO 2 reduction. Compared to carboxyl dopants,t he sulfoxide dopants further improved the electron communication between NapCo and graphene,which led to the increase of turnover frequency of the Co sites by about 3times for CO production with aF aradic efficiency up to 97 %. Pristine NapCo in the absence of agraphene support did not displaye fficient electron communication with the electrode and thus failed to serve as the electrochemical active site for CO 2 reduction under the identical conditions.

Bi2O3/BiO2 Nanoheterojunction for Highly Efficient Electrocatalytic CO2 Reduction to Formate

“…By integrating with multifunctional structures, heterostructure engineering is a powerful means to steer the reaction pathway in various catalytic processes. − Coupling the heterostructure interfaces to achieve synergistic catalytic effects plays a pivotal role in regulating the electron transfer, geometric structure, and interfacial coordination environment, thus alleviating the energy barriers of critical reaction intermediates ECO 2 RR. − Nevertheless, Bi-based catalysts have been widely accepted to be reduced to metallic Bi functioned as the active site during ECO 2 RR. − Based on these premises, an interesting question arises: How does the structure evolve on Bi-based heterojunctions under ECO 2 RR conditions, and do the heterostructures thoroughly transferred to the metallic Bi or partially preserved? Up to now, rare research has been devoted to unraveling the dynamic structure evolution of Bi-based heterostructure catalysts.…”

Superficial Hydroxyl and Amino Groups Synergistically Active Polymeric Carbon Nitride for CO2 Electroreduction

“…Simultaneously, the absorbance peak of 12 CO (∼1800 cm −1 ) was absent in Figure 4f even at high potential, suggesting that CO quickly desorbed from catalyst surface and thus COOH* generation was the rate-limiting step. 43,44 In summary, we presented a facile thermal treatment method to produce ultrathin porous PCN nanosheets modified by superficial hydroxyl and amino groups. The as-obtained OA-PCN showed exclusive CO 2 -EC selectivity for CO…”

Surface modification of metal materials for high-performance electrocatalytic carbon dioxide reduction

“…[196][197][198] Meanwhile, porphyrins can strongly coordinate with different kinds of metal ions to form metal-porphyrin complexes, which are catalytically active and have attracted extensive attention in many catalytic reactions. [199][200][201][202] Recently, both kinds of porphyrin derivatives (i.e., porphyrins and metal-porphyrin complexes) were found to be effective surface modifiers of metal materials to improve their catalytic performance in many chemical reactions; e.g., CO 2 RR. 159,167,200,201 Surface functionalization of metal materials with porphyrins could decrease the formation energy barriers of specific CO 2 -reduction intermediates, and thereby improve the catalytic activity and selectivity of metal materials toward CO 2 RR.…”

“…[199][200][201][202] Recently, both kinds of porphyrin derivatives (i.e., porphyrins and metal-porphyrin complexes) were found to be effective surface modifiers of metal materials to improve their catalytic performance in many chemical reactions; e.g., CO 2 RR. 159,167,200,201 Surface functionalization of metal materials with porphyrins could decrease the formation energy barriers of specific CO 2 -reduction intermediates, and thereby improve the catalytic activity and selectivity of metal materials toward CO 2 RR. 167 As a typical work, Cao et al 167 used a porphyrin ligand (denoted as P1; please see its chemical structure in Figure 10A) to functionalize the surface of Au NPs via a ligand exchange method, and studied their CO 2 -reduction performance.…”