Formation of (Rh–Fe)–FeOx Complex Sites Enables Methanol Synthesis from CO2

Zhu, Yifeng; Luo, Ran; Shi, Honghong; Koh, Katherine; Kovarik, Libor; Fulton, John L.; Lercher, Johannes A.; Zhao, Zhi-Jian; Gong, Jinlong; Gutiérrez, Oliver Y.

doi:10.1021/acscatal.4c00339

Formation of (Rh–Fe)–FeO_x Complex Sites Enables Methanol Synthesis from CO₂

Journal Article · Wed Jun 19 00:00:00 EDT 2024 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.4c00339· OSTI ID:2407052

Zhu, Yifeng ^[1]; Luo, Ran ^[2]; Shi, Honghong ^[1]; Koh, Katherine ^[1]; Kovarik, Libor ^[1]; ^[1]; Lercher, Johannes A. ^[1]; ^[2]; ^[2]; ^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Tianjin Univ. (China)

Here, we addressed the challenges of designing catalysts for selective CO₂ hydrogenation by incorporating oxide Fe species onto Rh nanoparticles. Nanoscopic FeO_x domains created a “reverse catalyst” structure (i.e., a metal oxide supported on a metal) that increased the density of interfacial sites compared to traditional supported catalysts. The contact between the metal nanoparticle and the oxide overlayer induced the formation of a surface Rh-Fe alloy that stabilize methoxy groups while suppressing hydrogenolysis to methane. Sites at FeO_x-metal interfaces interact with CO₂ sevenfold stronger than sites on metal surfaces, show larger energy barriers to cleave the C-O bonds, and offer a barrierless pathway for hydrogenation of methoxy species to methanol. Consequently, the multifunctional sites over FeO_x/Rh-Fe catalysts highlight and meet the requirements of a selective methanol catalyst: strong interaction with CO₂ to ensure high density of transition states; metal sites to activate and make hydrogen available to surface intermediates; and high energy barriers for C-O bond cleavage to form carbides. These synthesis and catalytic chemistries, demonstrated for Rh-Fe-FeO_x interfaces, enable us to overcome the limitations to the design of methanol production catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830

OSTI ID:: 2407052

Report Number(s):: PNNL-SA--199381

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 13 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 conversion
bimetallic catalysts
heterogeneous catalysis
methanol synthesis
multifunctional catalyst

Formation of (Rh–Fe)–FeOx Complex Sites Enables Methanol Synthesis from CO2

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Formation of (Rh–Fe)–FeO_x Complex Sites Enables Methanol Synthesis from CO₂