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CO2 Hydrogenation On Cu-catalysts Generated From ZnII Single-sites: Enhanced CH3OH Selectivity Compared To Cu/ZnO/Al2O3

Erwin Lam, Gina Noh, Kim Larmier, O. Safonova, C. Copéret
Published 2020 · Chemistry

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Abstract The hydrogenation of CO2 to CH3OH is mostly performed by a catalyst consisting mainly of copper and zinc (Cu/ZnO/Al2O3). Here, Cu-Zn based catalysts are generated using surface organometallic chemistry (SOMC) starting from a material consisting of isolated ZnII surface sites dispersed on SiO2 – ZnII@SiO2. Grafting of [Cu(OtBu)]4 on the surface silanols available on ZnII@SiO2 followed by reduction at 500 °C under H2 generates CuZnx alloy nanoparticles with remaining ZnII sites according to X-ray absorption spectroscopy (XAS). This Cu-Zn/SiO2 material displays high catalytic activity and methanol selectivity, in particular at higher conversion compared to benchmark Cu/ZnO/Al2O3 and most other catalysts. In situ XAS shows that CuZnx alloy is partially converted into Cu(0) and Zn(II) under reaction conditions, while ex situ solid state nuclear magnetic resonance and infrared spectroscopic studies only indicate the presence of methoxy species and no formate intermediates are detected, in contrast to most Cu-based catalysts. The absence of formate species is consistent with the higher methanol selectivity as recently found for the related Cu-Ga/SiO2.
This paper references
10.1016/J.JCAT.2015.01.021
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
A. Valant (2015)
10.1021/acs.jpclett.6b01328
Surface Sites in Cu-Nanoparticles: Chemical Reactivity or Microscopy?
Kim Larmier (2016)
10.1002/anie.201411581
Formation of a ZnO overlayer in industrial Cu/ZnO/Al2 O3 catalysts induced by strong metal-support interactions.
T. Lunkenbein (2015)
10.1021/JP201839S
Dynamic Cu/Zn Interaction in SiO2 Supported Methanol Synthesis Catalysts Unraveled by in Situ XAFS
D. Grandjean (2011)
10.1021/JA01269A023
ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS
S. Brunauer (1938)
10.1021/acs.chemrev.6b00816
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes
A. Alvarez (2017)
10.1023/A:1015326726898
Effects of Zirconia Phase on the Synthesis of Methanol over Zirconia-Supported Copper
K. Jung (2002)
10.1002/ZAAC.201300356
How to Prepare a Good Cu/ZnO Catalyst or the Role of Solid State Chemistry for the Synthesis of Nanostructured Catalysts
M. Behrens (2013)
10.1126/science.aaf0718
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis
Sebastian Kuld (2016)
10.1002/anie.201311073
Quantification of zinc atoms in a surface alloy on copper in an industrial-type methanol synthesis catalyst.
Sebastian Kuld (2014)
10.1021/ACS.ORGANOMET.8B00202
Alkyne Hydroamination Catalyzed by Silica-Supported Isolated Zn(II) Sites
A. K. Cook (2018)
10.1126/science.1219831
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
M. Behrens (2012)
10.1039/C3CY00573A
New and revisited insights into the promotion of methanol synthesis catalysts by CO2
O. Martin (2013)
10.1021/acs.jpcc.9b09631
CO2 Hydrogenation to CH3OH on Supported Cu Nanoparticles: Nature and Role of Ti in Bulk Oxides vs Isolated Surface Sites
Gina Noh (2019)
10.1002/anie.201204995
Towards oil independence through renewable methanol chemistry.
G. Olah (2013)
10.1021/jacs.8b05595
Isolated Zr Surface Sites on Silica Promote Hydrogenation of CO2 to CH3OH in Supported Cu Catalysts.
Erwin Lam (2018)
10.1126/science.aal3573
Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts
Shyam Kattel (2017)
10.1021/acs.accounts.9b00138
Single-Sites and Nanoparticles at Tailored Interfaces Prepared via Surface Organometallic Chemistry from Thermolytic Molecular Precursors.
C. Copéret (2019)
10.1021/JA9537639
Molecular and polymer precursor routes to manganese-doped zinc orthosilicate phosphors
Kai Su (1996)
10.1038/s41560-019-0491-2
Fuels and energy carriers from single-site catalysts prepared via surface organometallic chemistry
C. Copéret (2019)
10.1016/J.JCAT.2015.04.035
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
Céline Tisseraud (2015)
10.1039/d0sc00465k
Enhanced CH 3 OH selectivity in CO 2 hydrogenation using Cu-based catalysts generated via SOMC from Ga III single-sites
Erwin Lam (2020)
10.1021/acs.chemrev.7b00435
Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment.
J. Artz (2018)
10.1039/c4cs00122b
Recycling of carbon dioxide to methanol and derived products - closing the loop.
Alain Goeppert (2014)
10.1023/A:1023588322846
On the Issue of the Active Site and the Role of ZnO in Cu/ZnO Methanol Synthesis Catalysts
J. Nakamura (2003)
10.1038/nature06949
High-resolution carbon dioxide concentration record 650,000–800,000 years before present
D. Lüthi (2008)
10.1002/cssc.201900134
Selective Hydrogenation of CO2 to CH3 OH on Supported Cu Nanoparticles Promoted by Isolated TiIV Surface Sites on SiO2.
Gina Noh (2019)
10.1002/cctc.201402278
Synthesis and Characterisation of a Highly Active Cu/ZnO:Al Catalyst
J. Schumann (2014)
10.1107/S1600577515018007
Quick-EXAFS setup at the SuperXAS beamline for in situ X-ray absorption spectroscopy with 10 ms time resolution
O. Müller (2016)
10.1016/0304-5102(90)85147-A
On the mechanism of CO and CO2 hydrogenation reactions on zirconia-supported catalysts: a diffuse reflectance FTIR study
C. Schild (1990)
10.1006/JCAT.2000.2881
Role of Hydrogen Spillover in Methanol Synthesis over Cu/ZrO2
K. Jung (2000)
10.1039/C2TC00796G
Cu nanoparticles on 2D and 3D silica substrates: controlled size and density, and critical size in catalytic silicon nanowire growth
A. Roussey (2013)
10.1002/cctc.201500123
The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu‐Based Catalysts
Felix Studt (2015)
10.1021/ACSCATAL.9B01943
CO2 Hydrogenation to Methanol over ZrO2-Containing Catalysts: Insights into ZrO2 Induced Synergy
Kongzhai Li (2019)
10.5194/ESD-7-327-2016
Differential climate impacts for policy-relevant limits to global warming: the case of 1.5 °C and 2 °C
C. Schleussner (2015)



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