Cobalt-Based Nonprecious Metal Catalysts Derived from Metal–Organic Frameworks for High-Rate Hydrogenation of Carbon Dioxide

Lu, Xiaofei; Liu, Yang; He, Yurong; Kuhn, Andrew N.; Shih, Pei-Chieh; Sun, Cheng-Jun; Wen, Xiaodong; Shi, Chuan; Yang, Hong

doi:10.1021/acsami.9b05645

Title: Cobalt-Based Nonprecious Metal Catalysts Derived from Metal–Organic Frameworks for High-Rate Hydrogenation of Carbon Dioxide

Journal Article · Fri Jul 12 00:00:00 EDT 2019 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.9b05645· OSTI ID:1573059

Lu, Xiaofei ^[1]; Liu, Yang ^[2]; He, Yurong ^[3]; Kuhn, Andrew N. ^[1]; Shih, Pei-Chieh ^[1]; Sun, Cheng-Jun ^[4];

^[3]; Shi, Chuan ^[5];

^[1]

Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Chemical and Biomolecular Engineering
Dalian Univ. of Technology, Dalian (China). State Key Lab. of Fine Chemicals, College of Chemistry
Chinese Academy of Sciences (CAS), Beijing (China). State Key Lab. of Coal Conversion, Inst. of Coal Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Chemical and Biomolecular Engineering; Dalian Univ. of Technology, Dalian (China). State Key Lab. of Fine Chemicals, College of Chemistry

The development of cost-effective catalysts with both high activity and selectivity for carbon–oxygen bond activation is a major challenge and has important ramifications for making value-added chemicals from carbon dioxide (CO₂). Herein, we present a one-step pyrolysis of metal organic frameworks that yields highly dispersed cobalt nanoparticles embedded in a carbon matrix which shows exceptional catalytic activity in the reverse water gas shift reaction. Incorporation of nitrogen into the carbon-based supports resulted in increased reaction activity and selectivity toward carbon monoxide (CO), likely because of the formation of a Mott–Schottky interface. At 300 °C and a high space velocity of 300 000 mL g^–1 h^–1, the catalyst exhibited a CO₂ conversion rate of 122 μmolCO₂ g^–1 s^–1, eight times higher than that of a reference Cu/ZnO/Al₂O₃ catalyst. Our experimental and computational results suggest that nitrogen-doping lowers the energy barrier for the formation of formate intermediates (CO₂* + H* → COOH* + *), in addition to the redox mechanism (CO₂* + * → CO* + O*). This enhancement is attributed to the efficient electron transfer at the cobalt–support interface, leading to higher hydrogenation activity and opening new avenues for the development of CO₂ conversion technology.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); Canadian Light Source; Chinese Scholarship Council; Univ. of Illinois at Urbana-Champaign, IL (United States)