Achieving Product Control in Furfural Hydrogenation Using Intermetallic Catalysts

Ward, Charles J.; Chen, Minda; Lamkins, Andrew; Ordonez, Claudio; Sun, Rong; Chatterjee, Puranjan; Niu, Minghui; Cui, Ruoyu; Liu, Da-Jiang; Huang, Wenyu

doi:10.1021/acscatal.4c04091

Title: Achieving Product Control in Furfural Hydrogenation Using Intermetallic Catalysts

Journal Article · 06 November 2024 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.4c04091 · OSTI ID:2498390

Ward, Charles J. ^[1];

^[2]; Lamkins, Andrew ^[1]; Ordonez, Claudio ^[3]; Sun, Rong ^[3];

^[1]; Niu, Minghui ^[3]; Cui, Ruoyu ^[3];

^[4];

^[1]

Ames Lab., and Iowa State Univ., Ames, IA (United States)
Thermo Fisher Scientific, Hillsboro, OR (United States)
Iowa State Univ., Ames, IA (United States)
Ames Laboratory (AMES), Ames, IA (United States)

Intermetallic nanoparticles (iNPs) have garnered much attention as effective catalysts, but the impact of tuning surface properties to induce steric effects is relatively unexplored. Here, we report on the strategy of governing steric hindrance in bimetallic catalysts as a method to alter product selectivity in furfural hydrogenation using Rh-based iNPs by varying the size of the secondary metal atoms. RhGa, RhIn, and RhBi nanoparticles were synthesized within confined mesoporous silica wells (MSWs) and assessed for the vapor-phase hydrogenation of furfural. RhGa and RhIn iNPs enable product control with an enhanced selectivity to furan and furfuryl alcohol (>90%) compared to the monometallic Rh@MSW. Adding Bi to Rh inhibits the transformation of furfural almost entirely. In situ diffuse reflectance infrared Fourier transform spectroscopy studies and density functional theory-based machine-learning accelerated molecular dynamics simulations reveal that the secondary metal’s identity strongly impacts the preferred furfural adsorption mode on the active sites, leading to the observed catalysis control. Further, the mesoporous silica shell of the RhM@MSW catalyst provides protection against NP aggregation under reaction and regeneration conditions, as supported by good stability during recycling studies.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

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

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 2498390

Report Number(s):: AL-J--662

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 22 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

Intermetallic Nanocrystals: Syntheses and Catalytic Applications Yan, Yucong; Du, Jingshan S.; Gilroy, Kyle D. Advanced Materials, Vol. 29, Issue 14 https://doi.org/10.1002/adma.201605997	journal	February 2017
Co₃O₄ Nanoparticles Supported on Mesoporous Carbon for Selective Transfer Hydrogenation of α,β‐Unsaturated Aldehydes Wang, Guang‐Hui; Deng, Xiaohui; Gu, Dong Angewandte Chemie International Edition, Vol. 55, Issue 37 https://doi.org/10.1002/anie.201604673	journal	July 2016
Total Hydrogenation of Furfural over a Silica‐Supported Nickel Catalyst Prepared by the Reduction of a Nickel Nitrate Precursor Nakagawa, Yoshinao; Nakazawa, Hiroya; Watanabe, Hideo ChemCatChem, Vol. 4, Issue 11 https://doi.org/10.1002/cctc.201200218	journal	July 2012
Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol by using Ultrasmall Rh Nanoparticles Embedded on Diamine‐Functionalized KIT‐6 Neeli, Chinna Krishna Prasad; Chung, Young‐Min; Ahn, Wha‐Seung ChemCatChem, Vol. 9, Issue 24 https://doi.org/10.1002/cctc.201701037	journal	November 2017
Sub‐5 nm Intermetallic Nanoparticles Confined in Mesoporous Silica Wells for Selective Hydrogenation of Acetylene to Ethylene Maligal‐Ganesh, Raghu V.; Pei, Yuchen; Xiao, Chaoxian ChemCatChem, Vol. 12, Issue 11 https://doi.org/10.1002/cctc.202000155	journal	April 2020
High-Temperature-Stable and Regenerable Catalysts: Platinum Nanoparticles in Aligned Mesoporous Silica Wells Xiao, Chaoxian; Maligal-Ganesh, Raghu V.; Li, Tao ChemSusChem, Vol. 6, Issue 10 https://doi.org/10.1002/cssc.201300524	journal	August 2013
Liquid-Phase Catalytic Transfer Hydrogenation of Furfural over Homogeneous Lewis Acid-Ru/C Catalysts Panagiotopoulou, Paraskevi; Martin, Nickolas; Vlachos, Dionisios G. ChemSusChem, Vol. 8, Issue 12 https://doi.org/10.1002/cssc.201500212	journal	May 2015
Selective Hydrogenation of Furfural: Pure Silica Supported Metal Catalysts Zhang, Min; Yang, Jing‐He ChemistrySelect, Vol. 7, Issue 9 https://doi.org/10.1002/slct.202200013	journal	March 2022
Recent progress in intermetallic nanocrystals for electrocatalysis: From binary to ternary to high‐entropy intermetallics Liu, Jiawei; Lee, Carmen; Hu, Yue SmartMat, Vol. 4, Issue 4 https://doi.org/10.1002/smm2.1210	journal	May 2023
Properties of Copper Chromite Catalysts in Hydrogenation Reactions Rao, R.; Dandekar, A.; Baker, R. T. K. Journal of Catalysis, Vol. 171, Issue 2 https://doi.org/10.1006/jcat.1997.1832	journal	October 1997
Hydrodeoxygenation of Furfural Over Supported Metal Catalysts: A Comparative Study of Cu, Pd and Ni Sitthisa, Surapas; Resasco, Daniel E. Catalysis Letters, Vol. 141, Issue 6 https://doi.org/10.1007/s10562-011-0581-7	journal	March 2011
Nickel-Catalysed Vapour-Phase Hydrogenation of Furfural, Insights into Reactivity and Deactivation MacIntosh, Kathryn L.; Beaumont, Simon K. Topics in Catalysis, Vol. 63, Issue 15-18 https://doi.org/10.1007/s11244-020-01341-9	journal	July 2020
The metal-surface selection rule for infrared spectra of molecules adsorbed on small metal particles Greenler, Robert G.; Snider, D. R.; Witt, Donald Surface Science, Vol. 118, Issue 3 https://doi.org/10.1016/0039-6028(82)90197-2	journal	June 1982
From biomass to furan through decarbonylation of furfural under mild conditions Lejemble, Philippe; Gaset, Antoine; Kalck, Philippe Biomass, Vol. 4, Issue 4 https://doi.org/10.1016/0144-4565(84)90039-8	journal	January 1984
In-situ DRIFTS study of CeO2 supported Rh catalysts for N2O decomposition Zhu, Haiyang; Li, Yuejin; Zheng, Xiaolai Applied Catalysis A: General, Vol. 571 https://doi.org/10.1016/j.apcata.2018.12.020	journal	February 2019
Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions Taylor, Martin J.; Durndell, Lee J.; Isaacs, Mark A. Applied Catalysis B: Environmental, Vol. 180 https://doi.org/10.1016/j.apcatb.2015.07.006	journal	January 2016
Towards industrial furfural conversion: Selectivity and stability of palladium and platinum catalysts under continuous flow regime Ouyang, Weiyi; Yepez, Alfonso; Romero, Antonio A. Catalysis Today, Vol. 308 https://doi.org/10.1016/j.cattod.2017.07.011	journal	June 2018
Furfural hydrogenation over Cu, Ni, Pd, Pt, Re, Rh and Ru catalysts: Ab initio modelling of adsorption, desorption and reaction micro-kinetics Šivec, Rok; Huš, Matej; Likozar, Blaž Chemical Engineering Journal, Vol. 436 https://doi.org/10.1016/j.cej.2022.135070	journal	May 2022
Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu–Fe catalyst Yan, Kai; Chen, Aicheng Fuel, Vol. 115 https://doi.org/10.1016/j.fuel.2013.06.042	journal	January 2014
Hydrogen-free hydrogenation of furfural to furfuryl alcohol and 2-methylfuran over Ni and Co-promoted Cu/γ-Al2O3 catalysts Kalong, Munsuree; Hongmanorom, Plaifa; Ratchahat, Sakhon Fuel Processing Technology, Vol. 214 https://doi.org/10.1016/j.fuproc.2020.106721	journal	April 2021
Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over Ni/CNTs and bimetallic Cu Ni/CNTs catalysts Liu, Lujie; Lou, Hui; Chen, Min International Journal of Hydrogen Energy, Vol. 41, Issue 33 https://doi.org/10.1016/j.ijhydene.2016.05.188	journal	September 2016
Deactivation mechanistic studies of copper chromite catalyst for selective hydrogenation of 2-furfuraldehyde Liu, Dongxia; Zemlyanov, Dmitry; Wu, Tianpin Journal of Catalysis, Vol. 299 https://doi.org/10.1016/j.jcat.2012.10.026	journal	March 2013
Theoretical and experimental studies of the adsorption geometry and reaction pathways of furfural over FeNi bimetallic model surfaces and supported catalysts Yu, Weiting; Xiong, Ke; Ji, Na Journal of Catalysis, Vol. 317 https://doi.org/10.1016/j.jcat.2014.06.025	journal	August 2014
A study of furfural decarbonylation on K-doped Pd/Al2O3 catalysts Zhang, Wei; Zhu, Yulei; Niu, Shasha Journal of Molecular Catalysis A: Chemical, Vol. 335, Issue 1-2 https://doi.org/10.1016/j.molcata.2010.11.016	journal	February 2011
Synthetically tuned electronic and geometrical properties of intermetallic compounds as effective heterogeneous catalysts Marakatti, Vijaykumar S.; Peter, Sebastian C. Progress in Solid State Chemistry, Vol. 52 https://doi.org/10.1016/j.progsolidstchem.2018.09.001	journal	December 2018
Alloying cobalt in Co–Fe–Al catalyst for achieving the selective conversion of furfural to cyclopentanone Shao, Yuewen; Wu, Jie; Zheng, Zhiyuan Renewable Energy, Vol. 195 https://doi.org/10.1016/j.renene.2022.06.068	journal	August 2022
Bio-fuels from thermochemical conversion of renewable resources: A review Goyal, H. B.; Seal, Diptendu; Saxena, R. C. Renewable and Sustainable Energy Reviews, Vol. 12, Issue 2 https://doi.org/10.1016/j.rser.2006.07.014	journal	February 2008
Hydrogenation and Hydrolysis of Furfural to Furfuryl Alcohol, Cyclopentanone, and Cyclopentanol with a Heterogeneous Copper Catalyst in Water Zhou, Xuyang; Feng, Zhipeng; Guo, Wanwan Industrial & Engineering Chemistry Research, Vol. 58, Issue 10 https://doi.org/10.1021/acs.iecr.8b06217	journal	February 2019
Catalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts Taylor, Martin J.; Jiang, Li; Reichert, Joachim The Journal of Physical Chemistry C, Vol. 121, Issue 15 https://doi.org/10.1021/acs.jpcc.7b01744	journal	April 2017
Exploring Furfural Catalytic Conversion on Cu(111) from Computation Shi, Yun; Zhu, Yulei; Yang, Yong ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00303	journal	June 2015
A Ship-in-a-Bottle Strategy To Synthesize Encapsulated Intermetallic Nanoparticle Catalysts: Exemplified for Furfural Hydrogenation Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian Wei ACS Catalysis, Vol. 6, Issue 3 https://doi.org/10.1021/acscatal.5b02281	journal	February 2016
Intermetallic Compounds: Promising Inorganic Materials for Well-Structured and Electronically Modified Reaction Environments for Efficient Catalysis Furukawa, Shinya; Komatsu, Takayuki ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b02603	journal	December 2016
Electrochemical Energy Conversion on Intermetallic Compounds: A Review Rößner, Leonard; Armbrüster, Marc ACS Catalysis, Vol. 9, Issue 3 https://doi.org/10.1021/acscatal.8b04566	journal	January 2019
A Control over Hydrogenation Selectivity of Furfural via Tuning Exposed Facet of Ni Catalysts Meng, Xiaoyu; Yang, Yusen; Chen, Lifang ACS Catalysis, Vol. 9, Issue 5 https://doi.org/10.1021/acscatal.9b00238	journal	April 2019
Influence of Highly Stable Ni²⁺ Species in Ni Phyllosilicate Catalysts on Selective Hydrogenation of Furfural to Furfuryl Alcohol Kuhaudomlap, Sasithorn; Mekasuwandumrong, Okorn; Praserthdam, Piyasan ACS Omega, Vol. 8, Issue 1 https://doi.org/10.1021/acsomega.2c03590	journal	September 2022
Single-Step Hydrogenolysis of Furfural to 1,2-Pentanediol Using a Bifunctional Rh/OMS-2 Catalyst Pisal, Devendra S.; Yadav, Ganapati D. ACS Omega, Vol. 4, Issue 1 https://doi.org/10.1021/acsomega.8b01595	journal	January 2019
Selective Production of Furan from Gas-Phase Furfural Decarbonylation on Ni-MgO Catalysts Jiménez-Gómez, Carmen P.; Cecilia, Juan A.; García-Sancho, Cristina ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 8 https://doi.org/10.1021/acssuschemeng.8b06155	journal	March 2019
Regio- and Chemoselective Hydrogenation of Dienes to Monoenes Governed by a Well-Structured Bimetallic Surface Miyazaki, Masayoshi; Furukawa, Shinya; Komatsu, Takayuki Journal of the American Chemical Society, Vol. 139, Issue 50 https://doi.org/10.1021/jacs.7b08792	journal	December 2017
Rhodium Catalyst Structural Changes during, and Their Impacts on the Kinetics of, CO Oxidation Marino, Silvia; Wei, Lai; Cortes-Reyes, Marina JACS Au, Vol. 3, Issue 2 https://doi.org/10.1021/jacsau.2c00595	journal	February 2023
Ensemble Effect Evidenced by CO Adsorption on the 3-Fold PdGa Surfaces Prinz, Jan; Gaspari, Roberto; Stöckl, Quirin S. The Journal of Physical Chemistry C, Vol. 118, Issue 23 https://doi.org/10.1021/jp501584f	journal	May 2014
High Structure Sensitivity of Vapor-Phase Furfural Decarbonylation/Hydrogenation Reaction Network as a Function of Size and Shape of Pt Nanoparticles Pushkarev, Vladimir V.; Musselwhite, Nathan; An, Kwangjin Nano Letters, Vol. 12, Issue 10 https://doi.org/10.1021/nl3023127	journal	September 2012
Liquefaction of biomass as a source of fuels or chemicals Miller, Ian J.; Fellows, S. Kevin Nature, Vol. 289, Issue 5796 https://doi.org/10.1038/289398a0	journal	January 1981
Biomass conversion: Lignin up for break-down Bruijnincx, Pieter C. A.; Weckhuysen, Bert M. Nature Chemistry, Vol. 6, Issue 12, p. 1035-1036 https://doi.org/10.1038/nchem.2120	journal	December 2014
In situ quantitative single-molecule study of dynamic catalytic processes in nanoconfinement Dong, Bin; Pei, Yuchen; Zhao, Fei Nature Catalysis, Vol. 1, Issue 2 https://doi.org/10.1038/s41929-017-0021-1	journal	January 2018
Performance and characterization of rhenium-modified Rh–Ir alloy catalyst for one-pot conversion of furfural into 1,5-pentanediol Liu, Sibao; Amada, Yasushi; Tamura, Masazumi Catal. Sci. Technol., Vol. 4, Issue 8 https://doi.org/10.1039/C4CY00161C	journal	January 2014
Probing the interaction of Rh, Co and bimetallic Rh–Co nanoparticles with the CeO ₂ support: catalytic materials for alternative energy generation Varga, E.; Pusztai, P.; Óvári, L. Physical Chemistry Chemical Physics, Vol. 17, Issue 40 https://doi.org/10.1039/C5CP03549J	journal	January 2015
Efficient and selective hydrogenation of biomass-derived furfural to cyclopentanone using Ru catalysts Fang, Ruiqi; Liu, Hongli; Luque, Rafael Green Chemistry, Vol. 17, Issue 8 https://doi.org/10.1039/C5GC01462J	journal	January 2015
How π back-donation quantitatively controls the CO stretching response in classical and non-classical metal carbonyl complexes Bistoni, Giovanni; Rampino, Sergio; Scafuri, Nicola Chemical Science, Vol. 7, Issue 2 https://doi.org/10.1039/C5SC02971F	journal	January 2016
A new approach for the preparation of well-defined Rh and Pt nanoparticles stabilized by phosphine-functionalized silica for selective hydrogenation reactions Llop Castelbou, J.; Szeto, K. C.; Barakat, W. Chemical Communications, Vol. 53, Issue 22 https://doi.org/10.1039/C6CC10338C	journal	January 2017
Well-structured bimetallic surface capable of molecular recognition for chemoselective nitroarene hydrogenation Furukawa, Shinya; Takahashi, Katsuya; Komatsu, Takayuki Chemical Science, Vol. 7, Issue 7 https://doi.org/10.1039/C6SC00817H	journal	January 2016
The selective hydrogenation of furfural over intermetallic compounds with outstanding catalytic performance Yang, Yusen; Chen, Lifang; Chen, Yudi Green Chemistry, Vol. 21, Issue 19 https://doi.org/10.1039/C9GC01119F	journal	January 2019
Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over a Rh-loaded carbon catalyst in aqueous solution under mild conditions Matsagar, Babasaheb M.; Hsu, Chang-Yen; Chen, Season S. Sustainable Energy & Fuels, Vol. 4, Issue 1 https://doi.org/10.1039/C9SE00681H	journal	January 2020
Ligand and ensemble effects in adsorption on alloy surfaces Liu, P.; Nørskov, J. K. Physical Chemistry Chemical Physics, Vol. 3, Issue 17 https://doi.org/10.1039/b103525h	journal	January 2001

Similar Records

A ship-in-a-bottle strategy to synthesize encapsulated intermetallic nanoparticle catalysts: Exemplified for furfural hydrogenation

Journal Article · 2016 · ACS Catalysis · OSTI ID:1240740

Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian Wei; +8 more

Correlating furfural reaction pathways with interactions between furfural and monometallic surfaces

Journal Article · 2018 · Catalysis Today · OSTI ID:1659738

Xiong, Ke; Chen, Jingguang G.

Catalytic Activity of Ti-based MXenes for the Hydrogenation of Furfural

Journal Article · 2020 · ChemCatChem · OSTI ID:1724462

Naguib, Michael; Tang, Wenjie; Browning, Katie L.; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DRIFTS
diffuse reflectance infrared Fourier transform spectroscopy
heterogeneous catalysis
intermetallic compounds
intermetallic nanoparticles
selective hydrogenation

Title: Achieving Product Control in Furfural Hydrogenation Using Intermetallic Catalysts

Citation Formats

References (53)

Similar Records

Related Subjects