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oai:figshare.com:article/34037331 2026-10-01T00:13:27Z category_1 category_4 category_7 category_15 category_21 category_873 category_931 category_135 portal_63 item_type_6 month_year_10_2026

Mechanistic Study of CO₂ Reduction in a Metal Nanoparticle/Ligand-Based Nanoconfined Pocket Asmita Jana (16485039) Maria Fonseca Guzman (25147134) Faezeh Habibzadeh (9345347) Chong Liu (450204) Peidong Yang (1266450) Ethan J. Crumlin (1273839) Jin Qian (35219) Biophysics Biochemistry Medicine Neuroscience Biotechnology Chemical Sciences not elsewhere classified Information Systems not elsewhere classified Computational Biology sup >*</ sup additional secondary interactions stabilizing key intermediates results systematically reveal hydrogen bonding network ag surface confined 2 </ sub modulating interfacial reactivity double ag confinement double ag systems hydrogen bonding double ag systematically evaluate controlling reactivity confinement distance three systems interfacial water requires electrocatalysts producing value metal nanoparticle mechanistic study holds promise high selectivity energy efficiency effective strategy determining step added chemicals Electrochemically reducing CO₂ holds promise for producing value-added chemicals. Achieving this requires electrocatalysts with high selectivity and energy efficiency. Nanopocket engineering enhances catalytic activity by modulating interfacial reactivity and stabilizing key intermediates, especially those involved in the rate-determining step. Here, we use density functional theory to systematically evaluate the CO₂ reduction reaction (CO₂RR) and the competing hydrogen evolution reaction (HER) on three systems: Ag surface without confinement, double Ag confinement, and Ag surface confined by a ligand in the absence and presence of interfacial water. We find that decreasing the confinement distance from 7 to 4 Å stabilizes CO₂RR intermediates over HER in the double Ag and Ag/ligand systems, due to additional secondary interactions, such as hydrogen bonding, in the latter. The hydrogen bonding network is further enhanced in the presence of interfacial water, resulting in increased ^*COOH stabilization over ^*H in Ag/ligand and double Ag systems at a 7 Å confinement distance. The increased stabilization of ^*COOH over ^*H can be attributed to the high selectivity and activity for CO₂RR in Ag/ligand catalysts. These results systematically reveal how nanoconfinement can be an effective strategy for controlling reactivity at the gas–liquid–solid interfaces toward highly selective CO₂RR. 2026-09-30T00:00:00Z Text Journal contribution 10.1021/jacs.6c11755.s001 https://figshare.com/articles/journal_contribution/Mechanistic_Study_of_CO_sub_2_sub_Reduction_in_a_Metal_Nanoparticle_Ligand-Based_Nanoconfined_Pocket/34037331 CC BY-NC 4.0