Co⁰−Co^δ+ Interface Double‐Site‐Mediated C−C Coupling for the Photothermal Conversion of CO₂ into Light Olefins

Abstract

Solar-driven CO 2 hydrogenation into multicarbon products is a highly desirable, but challenging reaction. The bottleneck of this reaction lies in the CÀ C coupling of C 1 intermediates. Herein, we construct the CÀ C coupling centre for C 1 intermediates via the in situ formation of Co 0 À Co δ + interface double sites on MgAl 2 O 4 (CoÀ CoO x /MAO). Our experimental and theoretical prediction results confirmed the effective adsorption and activation of CO 2 by the Co 0 site to produce C 1 intermediates, while the introduction of the electron-deficient state of Co δ + can effectively reduce the energy barrier of the key CHCH* intermediates. Consequently, CoÀ CoO x /MAO exhibited a high C 2-4 hydrocarbons production rate of 1303 μmol g À 1 h À 1 ; the total organic carbon selectivity of C 2-4 hydrocarbons is 62.5 % under light irradiation with a high ratio ( � 11) of olefin to paraffin. This study provides a new approach toward the design of photocatalysts used for CO 2 conversion into C 2 + products.

Photothermal catalytic C1 conversion on supported catalysts

“…Co–CoO x /MgAl 2 O 4 achieved a C 2–4 yield of 1303 μmol g −1 h −1 under light irradiation. 118 The selectivity of C 2–4 total organic carbon reached 62.5%, and the ratio of olefin to alkane reached approximately 11. Experimental and theoretical results confirmed that the two active sites at the interface effectively adsorbed and activated CO 2 to form C1 intermediates through the Co 0 site.…”

Ruthenium–Cobalt Solid-Solution Alloy Nanoparticles for Enhanced Photopromoted Thermocatalytic CO2 Hydrogenation to Methane

“…13,14 The widespread applications of this technology necessitates an effective catalyst that simultaneously fulfills the requirement of high activity, exceptional durability, and cost-effectiveness to satisfy practical requirements. 15 For this purpose, a diverse range of materials have been investigated as potential catalysts for photopromoted CO 2 hydrogenation, including noble metals (e.g., Ir, Ru, Pt, and Pd) 16−19 or nonprecious metals (e.g., Cu, Co, and Ni) 14,20,21 deposited on various supports. Among these catalysts, Ru-based nanomaterials have garnered extensive recognition as the most promising catalysts for catalytic CO 2 methanation; however, the limited availability and cost-prohibitive nature of Ru pose significant constraints on their practical industrial applications.…”

“…On the other hand, photopromoted thermocatalytic CO 2 reduction, employing green H 2 derived from renewable energy sources, for the production of fuels or chemicals under mild conditions presents a promising pathway to effectively alleviate global warming and mitigate energy scarcity issues. , The widespread applications of this technology necessitates an effective catalyst that simultaneously fulfills the requirement of high activity, exceptional durability, and cost-effectiveness to satisfy practical requirements . For this purpose, a diverse range of materials have been investigated as potential catalysts for photopromoted CO 2 hydrogenation, including noble metals (e.g., Ir, Ru, Pt, and Pd) − or nonprecious metals (e.g., Cu, Co, and Ni) ,, deposited on various supports. Among these catalysts, Ru-based nanomaterials have garnered extensive recognition as the most promising catalysts for catalytic CO 2 methanation; however, the limited availability and cost-prohibitive nature of Ru pose significant constraints on their practical industrial applications. , In this context, the incorporation of a nonprecious transition metal into Ru-forming alloys to mitigate Ru consumption represents an appealing strategy.…”