Electroreduction of Carbon Dioxide in Metallic Nanopores through a Pincer Mechanism

Abstract

Metallic catalysts with nanopores are advantageous on improving both activity and selectivity,w hile the reason behind that remains unclear all along. In this work, porous Zn nanoparticles (P-Zn) were adopted as am odel catalyst to investigate the catalytic behavior of metallic nanopores.Insitu X-ray absorption spectroscopy, in situ Fourier transform infrared spectroscopy, and density functional theory (DFT) analyses reveal that the concave surface of nanopores works like ap incer to capture and clamp CO 2 and H 2 Op recursors simultaneously,t hus lowering the energy barriers of CO 2 electroreduction. Resultantly,t he pincer mechanism endows P-Zn with ah igh Faradic efficiency (98.1 %) towards CO production at the potential of À0.95 Vv s. RHE. Moreover, DFT calculation demonstrates that Co and Cu nanopores exhibit the pincer behavior as well, suggesting that this mechanism is universal for metallic nanopores.

A General Concurrent Template Strategy for Ordered Mesoporous Intermetallic Nanoparticles with Controllable Catalytic Performance

“…In contrast, when catalyzed by Pt 1 Sn 1 @KIT‐6, ≈80 % of 3‐NS and ≈16 % of 3‐AS were achieved under the same conditions. Obviously, crystalline mesoporous framework slightly enhanced catalytic selectivity of intermetallic Pt 1 Sn 1 toward favorable 3‐NS, possibly because crystalline mesoporosity provided a “pincer” environment for selective catalysis [8a] . Meanwhile, both Pt and Pt 1 Sn 1 nanoparticles gradually deactivated during catalysis, because of well‐known Ostwald ripening process.…”

Recent Advances of the Confinement Effects Boosting Electrochemical CO2 Reduction

“…Nano porous materials were widely used in electrocatalysis because of their large specific surface area and thus the large number of active sites. [17] In addition to the enormous surface area of porous materials, their unique structure-induced confinement effect is also an important factor in facilitating the catalytic performance in CO 2 RR.…”

Precise Synthesis of Hollow Mesoporous Palladium–Sulfur Alloy Nanoparticles for Selective Catalytic Hydrogenation

“…[28][29][30][31][32] In electrocatalysis, both mesopores and nanocavities have been demonstrated to modify geometric structures that further optimize the electronic and steric effects of the catalysts and thus enhance the product selectivity to some content. 23,[33][34][35][36][37][38] However, limited success has been achieved in applying the geometric effect of (hollow) mesoporous metals to adjust the selectivity of the products in hydrogenation reactions, although supported metal nanoclusters within mesoporous matrixes have been studied to enhance catalytic activity. [39][40][41] Hollow mesoporous metal nanocrystals were synthesized through templating strategies.…”