Thiacalix[4]arene-Stabilized Sb/Ag Bimetallic Nanoclusters: Elucidating the Effects of Sb Doping on Electrocatalytic CO2 Reduction in Ag Clusters.

Accurately identifying the metal doping effects within heterogeneous catalysts presents a formidable challenge due to the complex nature of controlling the interfacial chemistry at the molecular level. Herein, we use two sets of atomically precise nanoclusters to demonstrate the impact of Sb doping on the electrocatalytic CO2 reduction activity in Ag nanoclusters. Leveraging the unique properties of the thiacalix[4]arene, we have pioneered a methodology for incorporating catalytic Ag1+ and Sb3+ sites, culminating in the synthesis of the pioneering Sb-Ag bimetallic cluster, Sb2Ag11. We refined this structure by replacing the two Sb3+ sites with Na+ sites, resulting in a Na2Ag10 cluster. Broadening our investigative scope, we isolated the core components from both Sb2Ag11 and Na2Ag10 and obtained two clusters: Sb2Ag4 and Ag4. The subtle compositional variations between two pairs of structurally analogous clusters, Sb2Ag11 and Na2Ag10, as well as Sb2Ag4 and Ag4, create opportunities to investigate how the Sb doping impacts the catalytic activity of Ag clusters. Clearly, compared to the undoped clusters, those doped with Sb exhibit higher catalytic current densities and enhanced CO selectivity. The theoretical calculations suggest that Sb doping can enhance the adsorption barrier of *H, thereby inhibiting hydrogen evolution activity and conversely promoting eCO2RR to CO activity.

Ag1+ incorporation via a Zr4+-anchored metalloligand: fine-tuning catalytic Ag sites in Zr/Ag bimetallic clusters for enhanced eCO2RR-to-CO activity.

Attaining meticulous dominion over the binding milieu of catalytic metal sites remains an indispensable pursuit to tailor product selectivity and elevate catalytic activity. By harnessing the distinctive attributes of a Zr4+-anchored thiacalix[4]arene (TC4A) metalloligand, we have pioneered a methodology for incorporating catalytic Ag1+ sites, resulting in the first Zr-Ag bimetallic cluster, Zr2Ag7, which unveils a dualistic configuration embodying twin {ZrAg3(TC4A)2} substructures linked by an {AgSal} moiety. This cluster unveils a trinity of discrete Ag sites: a pair ensconced within {ZrAg3(TC4A)2} subunits and one located between two units. Expanding the purview, we have also crafted ZrAg3 and Zr2Ag2 clusters, meticulously mimicking the two Ag site environment inherent in the {ZrAg3(TC4A)2} monomer. The distinct structural profiles of Zr2Ag7, ZrAg3, and Zr2Ag provide an exquisite foundation for a precise comparative appraisal of catalytic prowess across three Ag sites intrinsic to Zr2Ag7. Remarkably, Zr2Ag7 eclipses its counterparts in the electroreduction of CO2, culminating in a CO faradaic efficiency (FECO) of 90.23% at -0.9 V. This achievement markedly surpasses the performance metrics of ZrAg3 (FECO: 55.45% at -1.0 V) and Zr2Ag2 (FECO: 13.09% at -1.0 V). Utilizing in situ ATR-FTIR, we can observe reaction intermediates on the Ag sites. To unveil underlying mechanisms, we employ density functional theory (DFT) calculations to determine changes in free energy accompanying each elementary step throughout the conversion of CO2 to CO. Our findings reveal the exceptional proficiency of the bridged-Ag site that interconnects paired {ZrAg3(TC4A)2} units, skillfully stabilizing *COOH intermediates, surpassing the stabilization efficacy of the other Ag sites located elsewhere. The invaluable insights gleaned from this pioneering endeavor lay a novel course for the design of exceptionally efficient catalysts tailored for CO2 reduction reactions, emphatically underscoring novel vistas this research unshrouds.