Developing catalysts with excellent CO2 capture capability and electrochemical CO2 reduction reaction (CO2RR) at a wide potential range simultaneously is significant but remains a formidable challenge. Here, two novel InMg defective trinuclear cluster-based MOFs (SNNU-41 and SNNU-42) with abundant p-block unsaturated coordinated sites were reported and exhibited good CO2 capture and CO2RR performance simultaneously. Due to the suitable micropores, SNNU-41 showed higher CO2 capture ability at different adsorption pressure conditions. On account of the rigid framework and the closer p band center to Fermi level, SNNU-42 accelerated the conversion of CO2 molecule to C1 efficiency. Notably, via adjusting the ratio of p-block metal (In) in the SNNU-42 framework, the performance of the CO2RR was promoted drastically. SNNU-42 with the InMg (1:1.8) mixed cluster delivered an excellent Faradaic efficiency of 91.3% for C1 products and high selectivity of 72.0% for HCOOH at −2.5 V (vs Ag/Ag+) with a total current density of 77.2 mA cm–2. This work provides a possibility for efficient CO2 capture and CO2RR electrocatalysts through the modulation of electronic structures and composition in MOFs.
Synthesis of high-loading single-atom catalysts (SACs) with unique coordination structures, especially those p -block main group metals (e.g., In, Sn), to realize electrocatalytic CO 2 reduction reaction (CO 2 RR) with high performance remains a challenge. Here, we report a complex-confinement strategy to prepare In–O 2 N 2 and In–O 4 SACs on hollow mesoporous nitrogen-doped carbon, with a loading amount as high as 13.02 wt% and 9.89 wt%, respectively. In–O 2 N 2 SACs outperform In–O 4 SACs in CO 2 RR toward formate production, reaching a high selectivity (95.5%) and partial current density of formate (−58.2 mA cm −2 ). In situ Raman spectroscopy shows that In–O 2 N 2 SACs have a sole ∗OCHO intermediate for formate product, whereas both ∗OCHO and ∗COOH intermediates are observed in In–O 4 SACs. Computational calculations elucidate that coordination environment matters greatly in the electronic structure manipulation of In SACs, where a closer position of p -band center to the Fermi level enables In–O 2 N 2 SACs to bind and activate CO 2 molecules more favorably.
Understanding sulfur conversion chemistry is key to the development of sulfur-based high-energy-density batteries. However, unclear relationships between the electronic structure of the catalyst and its activity are the major problem. Here, we provide a direct correlation between the p electron gain of S in p -block metal sulfides and the apparent activation energies ( E a ) for the sulfur reduction reaction (SRR), in particular, Li 2 S n to Li 2 S conversion, which is the rate-determining step of the SRR. The maximum p charge occurs in bismuth sulfide and results in the lowest E a and a high SRR rate in the cathode. Li–S batteries with the Bi 2 S 3 catalyst work steadily at a high rate of 5.0C with a high-capacity retention of ~85% after 500 cycles. A high areal capacity of ~21.9 mAh cm −2 was obtained under a high sulfur loading of 17.6 mg cm −2 but a low electrolyte/sulfur ratio of 7.5 μl mg −1 .
危险品化学品经营许可证（带存储）