Roles of Cu+ and Cu0 sites in liquid-phase hydrogenation of esters on core-shell CuZnx@C catalysts

Yao, Yaqi; Wu, Xiaoqian; Gutiérrez-Tinoco, Oliver Y.; Ji, Jing; Jin, Peng; Wang, Shengnian; Xu, Yan; Zhao, Yujun; Wang, Shengping; Ma, Xinbin; Lercher, Johannes A.

doi:10.1016/j.apcatb.2020.118698

Title: Roles of Cu⁺ and Cu⁰ sites in liquid-phase hydrogenation of esters on core-shell CuZn_x@C catalysts

Journal Article · 31 January 2020 · Applied Catalysis B: Environmental

DOI: https://doi.org/10.1016/j.apcatb.2020.118698 · OSTI ID:1599412

Yao, Yaqi ^[1]; Wu, Xiaoqian ^[1];

^[2]; Ji, Jing ^[3]; Jin, Peng ^[3]; Wang, Shengnian ^[4]; Xu, Yan ^[1];

^[5];

^[1]; Ma, Xinbin ^[1];

^[6]

Tianjin Univ. (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
Hebei Univ. of Technology, Tianjin (China)
Louisiana Tech Univ., Ruston, LA (United States)
Tianjin Univ. (China); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Technische Univ. Munchen, Garching (Germany)

Liquid-phase hydrogenolytic reduction of esters on Cu-based catalysts is a promising approach for synthesis of alcohols. Here, in this work, core-shell CuZn_x@C materials synthesized via pyrolysis of a Zn(NO₃)₂-loaded metal-organic framework (MOF) were proposed, in which well-defined spacing between Cu species in the parent MOF and the homogeneous loading of a Zn salt leads to an ideal distribution and strong interaction of Cu and Zn after pyrolysis of the precursor. The as-synthesized CuZn_x@C showed a much higher catalytic activity than Cu@C. This higher activity is tentatively attributed to the simultaneous presence of Cu⁰ and Cu⁺ sites at ZnO crystal domains. The resulting Cu-O-Zn sites have a high tendency to adsorb the ester in the form of a surface bound species that greatly improves the hydrogenolysis, which is the rate controlling step in the reductive pathway. A theoretical study confirms the ability of this site to bind and catalytically convert fatty acid esters.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: China Scholarship Council (CSC); National Natural Science Foundation of China (NSFC); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1599412

Report Number(s):: PNNL-SA-149387

Journal Information:: Applied Catalysis B: Environmental, Journal Name: Applied Catalysis B: Environmental Journal Issue: C Vol. 267; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Hydrogenation of methyl acetate to ethanol by Cu/ZnO catalyst encapsulated in SBA-15 Wang, Yue; Liao, Junyu; Zhang, Jian AIChE Journal, Vol. 63, Issue 7 https://doi.org/10.1002/aic.15620	journal	January 2017
Stabilization of Copper Catalysts for Liquid-Phase Reactions by Atomic Layer Deposition O'Neill, Brandon J.; Jackson, David H. K.; Crisci, Anthony J. Angewandte Chemie International Edition, Vol. 52, Issue 51 https://doi.org/10.1002/anie.201308245	journal	November 2013
Inside Cover: Facile Synthesis of Cu@CeO ₂ and Its Catalytic Behavior for the Hydrogenation of Methyl Acetate to Ethanol (ChemCatChem 12/2017) Wang, Yue; Zhao, Yujun; Lv, Jing ChemCatChem, Vol. 9, Issue 12 https://doi.org/10.1002/cctc.201700823	journal	June 2017
Selective hydrogenation of fatty acids and methyl esters of fatty acids to obtain fatty alcohols-a review: Production of fatty alcohols by selective hydrogenation Sánchez, María A.; Torres, Gerardo C.; Mazzieri, Vanina A. Journal of Chemical Technology & Biotechnology, Vol. 92, Issue 1 https://doi.org/10.1002/jctb.5039	journal	July 2016
Characterization of CuO-ZnO catalysts by X-ray photoelectron spectroscopy: Precursors, calcined and reduced samples Moretti, G.; Fierro, G.; Lo Jacono, M. Surface and Interface Analysis, Vol. 14, Issue 6-7 https://doi.org/10.1002/sia.740140609	journal	June 1989
New entries in the XPS fingerprint database for the characterization of precipitated Cu?Zn?Al oxide catalysts Grohmann, I.; Peplinski, B.; Unger, W. Surface and Interface Analysis, Vol. 19, Issue 1-12 https://doi.org/10.1002/sia.7401901110	journal	June 1992
Deactivation Mechanism of Cu/Zn Catalyst Poisoned by Organic Chlorides in Hydrogenation of Fatty Methyl Ester to Fatty Alcohol Huang, Hui; Wang, Shaohong; Wang, Shujia Catalysis Letters, Vol. 134, Issue 3-4 https://doi.org/10.1007/s10562-009-0247-x	journal	December 2009
Structure and catalytic activity of phosphine-substituted ruthenium carbonyl carboxylates Matteoli, Ugo; Menchi, Gloria; Bianchi, Mario Journal of Organometallic Chemistry, Vol. 498, Issue 2 https://doi.org/10.1016/0022-328X(95)05518-T	journal	August 1995
Alcohol synthesis by hydrogenation of fatty acid methyl esters on supported Ru–Sn and Rh–Sn catalysts Miyake, Takanori; Makino, Takahiko; Taniguchi, Shin-ichi Applied Catalysis A: General, Vol. 364, Issue 1-2 https://doi.org/10.1016/j.apcata.2009.05.036	journal	July 2009
The influence of B-doping on the catalytic performance of Cu/HMS catalyst for the hydrogenation of dimethyloxalate Yin, Anyuan; Qu, Jingwen; Guo, Xiaoyang Applied Catalysis A: General, Vol. 400, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.04.011	journal	June 2011
A Ru-Sn-Co/AlO(OH) as a highly efficient catalyst for hydrogenation of dimethyl adipate to 1,6-hexanodiol in aqueous phase Jiang, Hong-Bin; Jiang, Hai-Jun; Su, Ke Applied Catalysis A: General, Vol. 447-448 https://doi.org/10.1016/j.apcata.2012.09.041	journal	December 2012
Effect of structure of CuO/ZnO/Al2O3 composites on catalytic performance for hydrogenation of fatty acid ester He, Limin; Cheng, Haiyang; Liang, Guanfeng Applied Catalysis A: General, Vol. 452 https://doi.org/10.1016/j.apcata.2012.11.039	journal	February 2013
Structure evolution of mesoporous silica supported copper catalyst for dimethyl oxalate hydrogenation Zhao, Yujun; Zhang, Yaqing; Wang, Yue Applied Catalysis A: General, Vol. 539 https://doi.org/10.1016/j.apcata.2017.04.001	journal	June 2017
Synthesis of Pt-Cu/SiO2 catalysts with different structures and their application in hydrodechlorination of 1,2-dichloroethane Wei, Xing; Wang, Ai-Qin; Yang, Xiao-Feng Applied Catalysis B: Environmental, Vol. 121-122 https://doi.org/10.1016/j.apcatb.2012.03.020	journal	June 2012
Metal-organic framework derived Cu/ZnO catalysts for continuous hydrogenolysis of glycerol Zheng, Liping; Li, Xuewen; Du, Weichen Applied Catalysis B: Environmental, Vol. 203 https://doi.org/10.1016/j.apcatb.2016.10.011	journal	April 2017
Fluorine-modified Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol Gao, Peng; Li, Feng; Zhan, Haijuan Catalysis Communications, Vol. 50 https://doi.org/10.1016/j.catcom.2014.03.006	journal	May 2014
Core–shell structured Cu@m-SiO 2 and Cu/ZnO@m-SiO 2 catalysts for methanol synthesis from CO 2 hydrogenation Yang, Haiyan; Gao, Peng; Zhang, Chen Catalysis Communications, Vol. 84 https://doi.org/10.1016/j.catcom.2016.06.010	journal	September 2016
Ni-containing Cu/SiO2 catalyst for the chemoselective synthesis of ethanol via hydrogenation of dimethyl oxalate Zhao, Yujun; Zhao, Shuo; Geng, Yaochen Catalysis Today, Vol. 276 https://doi.org/10.1016/j.cattod.2016.01.053	journal	November 2016
Highly efficient heterogeneous catalytic materials derived from metal-organic framework supports/precursors Zhao, Shu-Na; Song, Xue-Zhi; Song, Shu-Yan Coordination Chemistry Reviews, Vol. 337 https://doi.org/10.1016/j.ccr.2017.02.010	journal	April 2017
CuNi@C catalysts with high activity derived from metal–organic frameworks precursor for conversion of furfural to cyclopentanone Wang, Yuan; Sang, Shengya; Zhu, Wei Chemical Engineering Journal, Vol. 299 https://doi.org/10.1016/j.cej.2016.04.068	journal	September 2016
Structural effects on trends in the deposition and dissolution of metal-supported metal adstructures Greeley, Jeffrey Electrochimica Acta, Vol. 55, Issue 20, p. 5545-5550 https://doi.org/10.1016/j.electacta.2010.04.055	journal	August 2010
Cu/SiO2 catalysts prepared by the ammonia-evaporation method: Texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol Chen, L.; Guo, P.; Qiao, M. Journal of Catalysis, Vol. 257, Issue 1 https://doi.org/10.1016/j.jcat.2008.04.021	journal	July 2008
Chemoselective synthesis of ethanol via hydrogenation of dimethyl oxalate on Cu/SiO 2 : Enhanced stability with boron dopant Zhao, Shuo; Yue, Hairong; Zhao, Yujun Journal of Catalysis, Vol. 297 https://doi.org/10.1016/j.jcat.2012.10.004	journal	January 2013
Silver-modulated SiO2-supported copper catalysts for selective hydrogenation of dimethyl oxalate to ethylene glycol Huang, Ying; Ariga, Hiroko; Zheng, Xinlei Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.07.006	journal	November 2013
The Cu–ZnO synergy in methanol synthesis from CO2, Part 1: Origin of active site explained by experimental studies and a sphere contact quantification model on Cu + ZnO mechanical mixtures Le Valant, Anthony; Comminges, Clément; Tisseraud, Céline Journal of Catalysis, Vol. 324 https://doi.org/10.1016/j.jcat.2015.01.021	journal	April 2015
The Cu–ZnO synergy in methanol synthesis from CO2, Part 2: Origin of the methanol and CO selectivities explained by experimental studies and a sphere contact quantification model in randomly packed binary mixtures on Cu–ZnO coprecipitate catalysts Tisseraud, Céline; Comminges, Clément; Belin, Thomas Journal of Catalysis, Vol. 330 https://doi.org/10.1016/j.jcat.2015.04.035	journal	October 2015
Hydrogenation of diesters on copper catalyst anchored on ordered hierarchical porous silica: Pore size effect Zhao, Yujun; Guo, Ziyuan; Zhang, Haojie Journal of Catalysis, Vol. 357 https://doi.org/10.1016/j.jcat.2017.11.006	journal	January 2018
Heterogeneous Cu2O-mediated ethylene glycol production from dimethyl oxalate Li, Lu; Ren, Dezhang; Fu, Jun Journal of Energy Chemistry, Vol. 25, Issue 3 https://doi.org/10.1016/j.jechem.2016.02.002	journal	May 2016
MOF derived porous carbon supported Cu/Cu 2 O composite as high performance non-noble catalyst Niu, Hongyun; Liu, Shuangliu; Cai, Yaqi Microporous and Mesoporous Materials, Vol. 219 https://doi.org/10.1016/j.micromeso.2015.07.027	journal	January 2016
Influence of the Support Material on the Activity and Selectivity of Ru–Sn–B Catalysts for the Selective Hydrogenation of Methyl Oleate Sánchez, María A.; Mazzieri, Vanina A.; Vicerich, María A. Industrial & Engineering Chemistry Research, Vol. 54, Issue 27 https://doi.org/10.1021/acs.iecr.5b01038	journal	June 2015
Hydrogenation of Dimethyl Oxalate over Copper-Based Catalysts: Acid–Base Properties and Reaction Paths Song, Yanbo; Zhang, Jian; Lv, Jing Industrial & Engineering Chemistry Research, Vol. 54, Issue 40 https://doi.org/10.1021/acs.iecr.5b01928	journal	September 2015
High Efficiency Cu-ZnO Hydrogenation Catalyst: The Tailoring of Cu-ZnO Interface Sites by Molecular Layer Deposition Zhang, Bin; Chen, Yao; Li, Jianwei ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01266	journal	August 2015
Insight into the Balancing Effect of Active Cu Species for Hydrogenation of Carbon–Oxygen Bonds Wang, Yue; Shen, Yongli; Zhao, Yujun ACS Catalysis, Vol. 5, Issue 10 https://doi.org/10.1021/acscatal.5b01678	journal	September 2015
Development of MOF-Derived Carbon-Based Nanomaterials for Efficient Catalysis Shen, Kui; Chen, Xiaodong; Chen, Junying ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01222	journal	August 2016
A copper-phyllosilicate core-sheath nanoreactor for carbon–oxygen hydrogenolysis reactions Yue, Hairong; Zhao, Yujun; Zhao, Shuo Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3339	journal	September 2013
Efficient hydrogenation of biomass-derived cyclic di-esters to 1,2-diols Balaraman, Ekambaram; Fogler, Eran; Milstein, David Chem. Commun., Vol. 48, Issue 8 https://doi.org/10.1039/C1CC15778G	journal	January 2012
Metal/metal oxide nanostructures derived from metal–organic frameworks Song, Yonghai; Li, Xia; Sun, Lanlan RSC Advances, Vol. 5, Issue 10 https://doi.org/10.1039/C4RA12273A	journal	January 2015
Selective hydrogenation of levulinate esters to 1,4-pentanediol using a ternary skeletal CuAlZn catalyst Ren, Dezhang; Wan, Xinyan; Jin, Fangming Green Chemistry, Vol. 18, Issue 22 https://doi.org/10.1039/C6GC02285E	journal	January 2016
Selective conversion of coconut oil to fatty alcohols in methanol over a hydrothermally prepared Cu/SiO ₂ catalyst without extraneous hydrogen Wu, Liubi; Li, Lulu; Li, Bolong Chemical Communications, Vol. 53, Issue 45 https://doi.org/10.1039/C7CC01126A	journal	January 2017
Remarkable enhancement of Cu catalyst activity in hydrogenation of dimethyl oxalate to ethylene glycol using gold Wang, Ya-nan; Duan, Xinping; Zheng, Jianwei Catalysis Science & Technology, Vol. 2, Issue 8 https://doi.org/10.1039/c2cy20154b	journal	January 2012
A Chemically Functionalizable Nanoporous Material [Cu₃(TMA)₂(H₂O)₃]_n Chui, Stephen S.-Y.; Lo, Samuel M.-F.; Charmant, Jonathan P. H. Science, Vol. 283, Issue 5405, p. 1148-1150 https://doi.org/10.1126/science.283.5405.1148	journal	February 1999
Active sites for CO ₂ hydrogenation to methanol on Cu/ZnO catalysts Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G. Science, Vol. 355, Issue 6331 https://doi.org/10.1126/science.aal3573	journal	March 2017
Ordered Mesoporous CuZn/HPS Catalysts for the Chemoselective Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol Zhao, Yujun; Guo, Ziyuan; Zhang, Haojie Chemistry Letters, Vol. 46, Issue 8 https://doi.org/10.1246/cl.170358	journal	August 2017
MOF-derived Cu@C Catalyst for the Liquid-phase Hydrogenation of Esters Zhao, Yujun; Wu, Xiaoqian; Zhou, Jiahua Chemistry Letters, Vol. 47, Issue 7 https://doi.org/10.1246/cl.180277	journal	July 2018

Similar Records

A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO₂ hydrogenation to methanol

Journal Article · 2024 · Nature Communications · OSTI ID:2405194

Ye, Runping; Ma, Lixuan; Mao, Jianing; +10 more

Operando high-pressure investigation of size-controlled CuZn catalysts for the methanol synthesis reaction

Journal Article · 2021 · Nature Communications · OSTI ID:1781589

Divins, Núria J.; Kordus, David; Timoshenko, Janis; +16 more

Enhanced Methanol Synthesis from CO₂ Hydrogenation Achieved by Tuning the Cu–ZnO Interaction in ZnO/Cu₂O Nanocube Catalysts Supported on ZrO₂ and SiO₂

Journal Article · 2024 · Journal of the American Chemical Society · OSTI ID:2471711

Kordus, David; Widrinna, Simon; Timoshenko, Janis; +7 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Roles of Cu+ and Cu0 sites in liquid-phase hydrogenation of esters on core-shell CuZnx@C catalysts

Citation Formats

References (44)

Similar Records

Related Subjects

Title: Roles of Cu⁺ and Cu⁰ sites in liquid-phase hydrogenation of esters on core-shell CuZn_x@C catalysts