Influence of support on Rh-Co bimetallic catalysts for ethylene hydroformylation

Porter, William N.; Kisslinger, Kim; Yuan, Yong; Chen, Jingguang G.

doi:10.1016/j.jcat.2024.115733

Influence of support on Rh-Co bimetallic catalysts for ethylene hydroformylation

Journal Article · Fri Aug 30 00:00:00 EDT 2024 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2024.115733· OSTI ID:2452785

^[1]; Kisslinger, Kim ^[2]; ^[3]; Chen, Jingguang G. ^[4]

Columbia Univ., New York, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Columbia Univ., New York, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Bimetallic Rh- and Co-based catalysts are promising materials for the heterogenous ethylene hydroformylation reaction. Here, in this study, the influence of a mesoporous silica (SBA-15) support on Rh and Co bimetallic interactions was investigated through a comparison with silica gel and alumina supports. The bimetallic catalyst supported on mesoporous silica (RhCo₃/SBA-15) showed the best C₃ oxygenate yield among the three bimetallic catalysts. In-situ vibrational studies suggested moderate binding of the gem-dicarbonyl and Rh(CO)(C₂H₄) intermediates due to this bimetallic interaction that led to improved hydroformylation performance. Kinetic studies revealed a lower hydroformylation barrier for the bimetallic compared to a Rh monometallic catalyst, and in-situ X-ray absorption spectroscopy investigations showed clear Rh-Co alloy formation on RhCo₃/SBA-15. The bimetallic enhancement effect from the interaction with the mesoporous silica support shown here can be further optimized to design olefin hydroformylation catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; SC0012653; SC0014664

OSTI ID:: 2452785

Alternate ID(s):: OSTI ID: 2440082

Report Number(s):: BNL--226212-2024-JAAM

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 438; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Hydroformylation of Olefins by a Rhodium Single-Atom Catalyst with Activity Comparable to RhCl(PPh ₃ ) ₃ Lang, Rui; Li, Tianbo; Matsumura, Daiju Angewandte Chemie International Edition, Vol. 55, Issue 52 https://doi.org/10.1002/anie.201607885	journal	November 2016
MOF‐Supported Heterogeneous Catalysts for Hydroformylation Reactions: A Minireview Samanta, Partha; Canivet, Jerome ChemCatChem, Vol. 16, Issue 7 https://doi.org/10.1002/cctc.202301435	journal	January 2024
Immobilized Catalysts for Hydroformylation Reactions: A Versatile Tool for Aldehyde Synthesis Neves, Ângela C. B.; Calvete, Mário J. F.; Pinho e. Melo, Teresa M. V. D. European Journal of Organic Chemistry, Vol. 2012, Issue 32 https://doi.org/10.1002/ejoc.201200709	journal	September 2012
Transient Response of Propionaldehyde Formation During CO/H2/C2H4 Reaction on Rh/SiO2 Balakos, M. W.; Chuang, S. S. C. Journal of Catalysis, Vol. 151, Issue 2 https://doi.org/10.1006/jcat.1995.1026	journal	February 1995
Confinement effect of rhodium(I) complex species on mesoporous MCM-41 and SBA-15: effect of pore size on the hydroformylation of 1-octene Vunain, Ephraim; Ncube, Phendukani; Jalama, Kalala Journal of Porous Materials, Vol. 25, Issue 1 https://doi.org/10.1007/s10934-017-0443-9	journal	May 2017
Mechanism of C₂₊ oxygenate synthesis on Rh catalysts Chuang, Steven S. C.; Stevens, Robert W.; Khatri, Rajesh Topics in Catalysis, Vol. 32, Issue 3-4, p. 225-232 https://doi.org/10.1007/s11244-005-2897-2	journal	March 2005
Gas-Phase Hydroformylation of Propene over Silica-Supported PPh3-Modified Rhodium Catalysts Kim, Taejin; Celik, Fuat E.; Hanna, David G. Topics in Catalysis, Vol. 54, Issue 5-7 https://doi.org/10.1007/s11244-011-9664-3	journal	February 2011
A mini review on strategies for heterogenization of rhodium-based hydroformylation catalysts Li, Cunyao; Wang, Wenlong; Yan, Li Frontiers of Chemical Science and Engineering, Vol. 12, Issue 1 https://doi.org/10.1007/s11705-017-1672-9	journal	September 2017
Vapour phase hydroformylation of ethylene and propene catalyzed by a rhodium-containing aluminum pillared smectite clay Lenarda, Maurizio; Ganzerla, Renzo; Storaro, Loretta Journal of Molecular Catalysis, Vol. 72, Issue 1 https://doi.org/10.1016/0304-5102(92)80032-C	journal	February 1992
Experimental investigation of ethylene hydroformylation to propanal on Rh and Co based catalysts Navidi, N.; Thybaut, J. W.; Marin, G. B. Applied Catalysis A: General, Vol. 469 https://doi.org/10.1016/j.apcata.2013.10.019	journal	January 2014
Heterogeneous hydroformylation of alkenes by Rh-based catalysts Liu, Boyang; Wang, Yu; Huang, Ning Chem, Vol. 8, Issue 10 https://doi.org/10.1016/j.chempr.2022.07.020	journal	October 2022
Enhancing regioselectivity via tuning the microenvironment in heterogeneous hydroformylation of olefins Zhang, Jing; Sun, Peng; Gao, Guang Journal of Catalysis, Vol. 387 https://doi.org/10.1016/j.jcat.2020.03.032	journal	July 2020
Confinement of atomically dispersed Rh catalysts within porous monophosphine polymers for regioselective hydroformylation of alkenes Zhao, Kang; Wang, Hongli; Wang, Xinzhi Journal of Catalysis, Vol. 401 https://doi.org/10.1016/j.jcat.2021.08.004	journal	September 2021
Can CO2-assisted alkane dehydrogenation lead to negative CO2 emissions? Biswas, Akash N.; Xie, Zhenhua; Chen, Jingguang G. Joule, Vol. 6, Issue 2 https://doi.org/10.1016/j.joule.2021.12.008	journal	February 2022
Comparison of direct and CO₂-oxidative dehydrogenation of propane Yuan, Yong; Porter, William N.; Chen, Jingguang G. Trends in Chemistry, Vol. 5, Issue 11, 840-852 https://doi.org/10.1016/j.trechm.2023.09.001	journal	November 2023
Insights into the Bimetallic Effects of a RhCo Catalyst for Ethene Hydroformylation: Experimental and DFT Investigations Huang, Ning; Liu, Boyang; Lan, Xiaocheng Industrial & Engineering Chemistry Research, Vol. 59, Issue 42 https://doi.org/10.1021/acs.iecr.0c03437	journal	September 2020
Heterogeneous Ligand-Free Rhodium Oxide Catalyst Embedded within Zeolitic Microchannel to Enhance Regioselectivity in Hydroformylation Liu, Cun; Zhang, Jingjing; Liu, Haiou Industrial & Engineering Chemistry Research, Vol. 58, Issue 47 https://doi.org/10.1021/acs.iecr.9b03598	journal	November 2019
Effect of Si/Al Ratio and Rh Precursor Used on the Synthesis of HY Zeolite-Supported Rhodium Carbonyl Hydride Complexes Khivantsev, Konstantin; Vityuk, Artem; Aleksandrov, Hristiyan A. The Journal of Physical Chemistry C, Vol. 119, Issue 30 https://doi.org/10.1021/acs.jpcc.5b03969	journal	July 2015
Theoretical Study of Ethylene Hydroformylation on Atomically Dispersed Rh/Al ₂ O ₃ Catalysts: Reaction Mechanism and Influence of the ReO _x Promoter Lee, Seungyeon; Patra, Abhirup; Christopher, Phillip ACS Catalysis, Vol. 11, Issue 15 https://doi.org/10.1021/acscatal.1c00705	journal	July 2021
Comparison of Heterogeneous Hydroformylation of Ethylene and Propylene over RhCo ₃ /MCM-41 Catalysts Mao, Zhongtian; Xie, Zhenhua; Chen, Jingguang G. ACS Catalysis, Vol. 11, Issue 23 https://doi.org/10.1021/acscatal.1c04359	journal	November 2021
Active Site Entropy of Atomically Dispersed Rh/Al₂O₃ Catalysts Dictates Activity for Ethylene Hydroformylation Zakem, Gregory; Christopher, Phillip ACS Catalysis, Vol. 13, Issue 8 https://doi.org/10.1021/acscatal.2c06321	journal	April 2023
Applied Hydroformylation Franke, Robert; Selent, Detlef; Börner, Armin Chemical Reviews, Vol. 112, Issue 11 https://doi.org/10.1021/cr3001803	journal	August 2012
Infrared Studies of Carbon Monoxide Chemisorbed on Rhodium Yang, C.; Garl, Carl W. The Journal of Physical Chemistry, Vol. 61, Issue 11 https://doi.org/10.1021/j150557a013	journal	November 1957
Ethene Hydroformylation Catalyzed by Rhodium Dispersed with Zinc or Cobalt in Silanol Nests of Dealuminated Zeolite Beta Qi, Liang; Das, Sonali; Zhang, Yanfei Journal of the American Chemical Society, Vol. 145, Issue 5 https://doi.org/10.1021/jacs.2c11075	journal	January 2023
Highly Efficient Heterogeneous Hydroformylation over Rh-Metalated Porous Organic Polymers: Synergistic Effect of High Ligand Concentration and Flexible Framework Sun, Qi; Dai, Zhifeng; Liu, Xiaolong Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/jacs.5b02122	journal	April 2015
Tandem Reactions of CO ₂ Reduction and Ethane Aromatization Gomez, Elaine; Nie, Xiaowa; Lee, Ji Hoon Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b08538	journal	October 2019
Prospects of Heterogeneous Hydroformylation with Supported Single Atom Catalysts Amsler, Jonas; Sarma, Bidyut B.; Agostini, Giovanni Journal of the American Chemical Society, Vol. 142, Issue 11 https://doi.org/10.1021/jacs.9b12171	journal	March 2020
Direct Observation of Kinetically Competent Surface Intermediates upon Ethylene Hydroformylation over Rh/Al ₂ O ₃ under Reaction Conditions by Time-Resolved Fourier Transform Infrared Spectroscopy Sivasankar, N.; Frei, H. The Journal of Physical Chemistry C, Vol. 115, Issue 15 https://doi.org/10.1021/jp112391n	journal	March 2011
Effect of Si/Al Ratio on the Nature and Reactivity of HY Zeolite-Supported Rhodium Dicarbonyl Complexes Vityuk, Artem; Aleksandrov, Hristiyan A.; Vayssilov, Georgi N. The Journal of Physical Chemistry C, Vol. 118, Issue 46 https://doi.org/10.1021/jp507526g	journal	November 2014
Ethene hydroformylation on Co/SiO₂ catalysts Kainulainen, T. A.; Niemelä, M. K.; Krause, A. O. I. Catalysis Letters, Vol. 53, Issue 1/2, p. 97-101 https://doi.org/10.1023/A:1019053805618	journal	January 1998
Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst Wang, Liangbing; Zhang, Wenbo; Wang, Shenpeng Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms14036	journal	December 2016
Rh single atoms on TiO2 dynamically respond to reaction conditions by adapting their site Tang, Yan; Asokan, Chithra; Xu, Mingjie Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12461-6	journal	October 2019
Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation Bauer, Gerald; Ongari, Daniele; Tiana, Davide Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14828-6	journal	February 2020
Reactions of CO2 and ethane enable CO bond insertion for production of C3 oxygenates Xie, Zhenhua; Xu, Yuanguo; Xie, Meng Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15849-x	journal	April 2020
Carbon dioxide reduction in tandem with light-alkane dehydrogenation Gomez, Elaine; Yan, Binhang; Kattel, Shyam Nature Reviews Chemistry, Vol. 3, Issue 11 https://doi.org/10.1038/s41570-019-0128-9	journal	September 2019
Bifunctional hydroformylation on heterogeneous Rh-WOx pair site catalysts Ro, Insoo; Qi, Ji; Lee, Seungyeon Nature, Vol. 609, Issue 7926 https://doi.org/10.1038/s41586-022-05075-4	journal	September 2022
Regioselective hydroformylation of propene catalysed by rhodium-zeolite Zhang, Xiangjie; Yan, Tao; Hou, Huaming Nature, Vol. 629, Issue 8012 https://doi.org/10.1038/s41586-024-07342-y	journal	April 2024
Chemically and electrochemically catalysed conversion of CO2 to CO with follow-up utilization to value-added chemicals Nielsen, Dennis U.; Hu, Xin-Ming; Daasbjerg, Kim Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0051-3	journal	April 2018
Continuous flow homogeneous hydroformylation of alkenes using supercritical fluids Webb, Paul B.; Kunene, Thulani E.; Cole-Hamilton, David J. Green Chemistry, Vol. 7, Issue 5 https://doi.org/10.1039/b416713a	journal	January 2005
Infrared spectroscopic investigation of the rhodium gem-dicarbonyl surface species Yates, John T.; Kolasinski, Kurt The Journal of Chemical Physics, Vol. 79, Issue 2 https://doi.org/10.1063/1.445844	journal	July 1983
Active sites for tandem reactions of CO ₂ reduction and ethane dehydrogenation Yan, Binhang; Yao, Siyu; Kattel, Shyam Proceedings of the National Academy of Sciences, Vol. 115, Issue 33 https://doi.org/10.1073/pnas.1806950115	journal	July 2018
Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds Zhuchkov, D. P.; Nenasheva, M. V.; Terenina, M. V. Petroleum Chemistry, Vol. 61, Issue 1 https://doi.org/10.1134/S0965544121010011	journal	November 2020
Current State of the Art of the Solid Rh-Based Catalyzed Hydroformylation of Short-Chain Olefins Hanf, Schirin; Alvarado Rupflin, Luis; Gläser, Roger Catalysts, Vol. 10, Issue 5 https://doi.org/10.3390/catal10050510	journal	May 2020

Similar Records

Catalysis by supported metal crystallites prepared from metal carbonyl clusters--3. Catalytic vapor-phase hydroformylation of olefins over Rh, bimetallic Rh-CO, and CO crystallites prepared from carbonyl cluster compounds dispersed on zinc oxide

Journal Article · Sun Dec 31 23:00:00 EST 1978 · J. Catal.; (United States) · OSTI ID:7138715

Controlling Reaction Pathways of Ethylene Hydroformylation Using Isolated Bimetallic Rhodium–Cobalt Sites

Journal Article · Sat Mar 29 00:00:00 EDT 2025 · Journal of the American Chemical Society · OSTI ID:2560705

Theoretical study of Rh/CO species

Journal Article · Thu Jun 30 00:00:00 EDT 1988 · J. Phys. Chem.; (United States) · OSTI ID:6333501

Related Subjects

58 GEOSCIENCES
Bimetallic interactions
Ethylene
Heterogeneous catalyst
Hydroformylation
Mesoporous support effect

Influence of support on Rh-Co bimetallic catalysts for ethylene hydroformylation

Citation Formats

References (43)

Similar Records

Related Subjects