Steering CO 2 hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces

Zhou, Chengshuang; Asundi, Arun S.; Goodman, Emmett D.; Hong, Jiyun; Werghi, Baraa; Hoffman, Adam S.; Nathan, Sindhu S.; Bent, Stacey F.; Bare, Simon R.; Cargnello, Matteo

doi:10.1073/pnas.2114768119

Title: Steering CO ₂ hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces

Journal Article · 07 February 2022 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.2114768119 · OSTI ID:1870809

^[1]; Asundi, Arun S. ^[1]; Goodman, Emmett D. ^[1]; Hong, Jiyun ^[2];

^[3]; Hoffman, Adam S. ^[2];

^[1]; Bent, Stacey F. ^[1];

^[3];

^[1]

Stanford Univ., CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

The conversion of CO₂ into fuels and chemicals is an attractive option for mitigating CO₂ emissions. Controlling the selectivity of this process is beneficial to produce desirable liquid fuels, but C–C coupling is a limiting step in the reaction that requires high pressures. Here, we propose a strategy to favor C–C coupling on a supported Ru/TiO₂ catalyst by encapsulating it within the polymer layers of an imine-based porous organic polymer that controls its selectivity. Such polymer confinement modifies the CO₂ hydrogenation behavior of the Ru surface, significantly enhancing the C₂₊ production turnover frequency by 10-fold. We demonstrate that the polymer layers affect the adsorption of reactants and intermediates while being stable under the demanding reaction conditions. Our findings highlight the promising opportunity of using polymer/metal interfaces for the rational engineering of active sites and as a general tool for controlling selective transformations in supported catalyst systems.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1870809

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 7 Vol. 119; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

An Isolated CO2 Adduct of a Nitrogen Base: Crystal and Electronic Structures Villiers, Claude; Dognon, Jean-Pierre; Pollet, Rodolphe Angewandte Chemie International Edition, Vol. 49, Issue 20 https://doi.org/10.1002/anie.201001035	journal	March 2010
A Tailored Microenvironment for Catalytic Biomass Conversion in Inorganic-Organic Nanoreactors Alamillo, Ricardo; Crisci, Anthony J.; Gallo, Jean Marcel R. Angewandte Chemie International Edition, Vol. 52, Issue 39 https://doi.org/10.1002/anie.201304693	journal	August 2013
Engineering Catalyst Microenvironments for Metal-Catalyzed Hydrogenation of Biologically Derived Platform Chemicals Schwartz, Thomas J.; Johnson, Robert L.; Cardenas, Javier Angewandte Chemie International Edition, Vol. 53, Issue 47 https://doi.org/10.1002/anie.201407615	journal	September 2014
Engineering of Ruthenium–Iron Oxide Colloidal Heterostructures: Improved Yields in CO ₂ Hydrogenation to Hydrocarbons Aitbekova, Aisulu; Goodman, Emmett D.; Wu, Liheng Angewandte Chemie International Edition, Vol. 58, Issue 48 https://doi.org/10.1002/anie.201910579	journal	November 2019
Controlling CO ₂ Hydrogenation Selectivity by Metal‐Supported Electron Transfer Li, Xiaoyu; Lin, Jian; Li, Lin Angewandte Chemie International Edition, Vol. 59, Issue 45 https://doi.org/10.1002/anie.202003847	journal	August 2020
Towards the room-temperature synthesis of covalent organic frameworks: a mini-review Bagheri, Ahmad Reza; Aramesh, Nahal Journal of Materials Science, Vol. 56, Issue 2 https://doi.org/10.1007/s10853-020-05308-9	journal	September 2020
Modifying the Surface Properties of Heterogeneous Catalysts Using Polymer-Derived Microenvironments Schwartz, Thomas J.; Wesley, Thejas S.; Dumesic, James A. Topics in Catalysis, Vol. 59, Issue 1 https://doi.org/10.1007/s11244-015-0501-y	journal	September 2015
Heterogeneous methanation: In situ infrared spectroscopic study of Ru/Al2O3 during the hydrogenation of CO Betta, R. Journal of Catalysis, Vol. 48, Issue 1-3 https://doi.org/10.1016/0021-9517(77)90082-3	journal	June 1977
Infrared studies of carbon monoxide hydrogenation over alumina-supported ruthenium Kellner, C. Journal of Catalysis, Vol. 71, Issue 2 https://doi.org/10.1016/0021-9517(81)90232-3	journal	October 1981
An infrared study of the influence of CO adsorption on the topology of supported ruthenium Solymosi, F. Journal of Catalysis, Vol. 115, Issue 1 https://doi.org/10.1016/0021-9517(89)90011-0	journal	January 1989
Chemistry of supported Ru: CO-induced oxidation of Ru at 310 K Robbins, J. Journal of Catalysis, Vol. 115, Issue 1 https://doi.org/10.1016/0021-9517(89)90012-2	journal	January 1989
Selective hydrogenation of citronellal to citronellol over Ru/TiO2 as compared to Ru/SiO2 Wismeijer, A. A.; Kieboom, A. P. G.; Van Bekkum, H. Applied Catalysis, Vol. 25, Issue 1-2 https://doi.org/10.1016/S0166-9834(00)81235-X	journal	August 1986
Influence of the oxide support reducibility on the CO2 methanation over Ru-based catalysts Dreyer, Jochen A. H.; Li, Peixin; Zhang, Linghai Applied Catalysis B: Environmental, Vol. 219 https://doi.org/10.1016/j.apcatb.2017.08.011	journal	December 2017
The effect of CO on CO2 methanation over Ru/Al2O3 catalysts: a combined steady-state reactivity and transient DRIFT spectroscopy study Falbo, Leonardo; Visconti, Carlo G.; Lietti, Luca Applied Catalysis B: Environmental, Vol. 256 https://doi.org/10.1016/j.apcatb.2019.117791	journal	November 2019
In-situ DRIFTS study of two-step CO2 capture and catalytic methanation over Ru,“Na2O”/Al2O3 Dual Functional Material Proaño, Laura; Tello, Edisson; Arellano-Trevino, Martha A. Applied Surface Science, Vol. 479 https://doi.org/10.1016/j.apsusc.2019.01.281	journal	June 2019
Kinetic study on carbon dioxide hydrogenation over Ru/γ-Al2O3 catalysts Kuśmierz, Marcin Catalysis Today, Vol. 137, Issue 2-4 https://doi.org/10.1016/j.cattod.2008.03.003	journal	September 2008
Kinetic modeling and transient DRIFTS–MS studies of CO2 methanation over Ru/Al2O3 catalysts Wang, Xiang; Hong, Yongchun; Shi, Hui Journal of Catalysis, Vol. 343 https://doi.org/10.1016/j.jcat.2016.02.001	journal	November 2016
Mechanism of CO2 reduction by H2 on Ru(0 0 0 1) and general selectivity descriptors for late-transition metal catalysts Avanesian, Talin; Gusmão, Gabriel S.; Christopher, Phillip Journal of Catalysis, Vol. 343 https://doi.org/10.1016/j.jcat.2016.03.016	journal	November 2016
CO2 hydrogenation reaction over pristine Fe, Co, Ni, Cu and Al2O3 supported Ru: Comparison and determination of the activation energies Mutschler, Robin; Moioli, Emanuele; Luo, Wen Journal of Catalysis, Vol. 366 https://doi.org/10.1016/j.jcat.2018.08.002	journal	October 2018
Ru/Al2O3 catalyzed CO2 hydrogenation: Oxygen-exchange on metal-support interfaces Yan, Yong; Wang, Qiaojuan; Jiang, Chunyang Journal of Catalysis, Vol. 367 https://doi.org/10.1016/j.jcat.2018.08.026	journal	November 2018
Kinetics of CO2 methanation over Ru/γ-Al2O3 and implications for renewable energy storage applications Duyar, Melis S.; Ramachandran, Arvind; Wang, Christine Journal of CO2 Utilization, Vol. 12 https://doi.org/10.1016/j.jcou.2015.10.003	journal	December 2015
Variations in activity of Ru/TiO2 and Ru/Al2O3 catalysts for CO2 hydrogenation: An investigation by in-situ infrared spectroscopy studies Dongapure, Pavan; Bagchi, Sayan; Mayadevi, S. Molecular Catalysis, Vol. 482 https://doi.org/10.1016/j.mcat.2019.110700	journal	February 2020
Mechanisms and kinetics of CO 2 hydrogenation to value-added products: A detailed review on current status and future trends Saeidi, Samrand; Najari, Sara; Fazlollahi, Farhad Renewable and Sustainable Energy Reviews, Vol. 80 https://doi.org/10.1016/j.rser.2017.05.204	journal	December 2017
Mechanistic Study of the Selective Methanation of CO over Ru/TiO ₂ Catalysts: Effect of Metal Crystallite Size on the Nature of Active Surface Species and Reaction Pathways Panagiotopoulou, Paraskevi; Verykios, Xenophon E. The Journal of Physical Chemistry C, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpcc.6b12091	journal	February 2017
Engineering the ZrO ₂ –Pd Interface for Selective CO ₂ Hydrogenation by Overcoating an Atomically Dispersed Pd Precatalyst Du, Yuan-Peng; Bahmanpour, Ali M.; Milošević, Luka ACS Catalysis, Vol. 10, Issue 20 https://doi.org/10.1021/acscatal.0c02146	journal	September 2020
Ru/TiO ₂ Catalysts with Size-Dependent Metal/Support Interaction for Tunable Reactivity in Fischer–Tropsch Synthesis Zhang, Yaru; Su, Xiong; Li, Lin ACS Catalysis, Vol. 10, Issue 21 https://doi.org/10.1021/acscatal.0c02780	journal	October 2020
ZrO ₂ Is Preferred over TiO ₂ as Support for the Ru-Catalyzed Hydrogenation of Levulinic Acid to γ-Valerolactone Ftouni, Jamal; Muñoz-Murillo, Ara; Goryachev, Andrey ACS Catalysis, Vol. 6, Issue 8 https://doi.org/10.1021/acscatal.6b00730	journal	July 2016
Design of Organic/Inorganic Hybrid Catalysts for Energy and Environmental Applications Goodman, Emmett D.; Zhou, Chengshuang; Cargnello, Matteo ACS Central Science, Vol. 6, Issue 11 https://doi.org/10.1021/acscentsci.0c01046	journal	October 2020
Active Site Dependent Reaction Mechanism over Ru/CeO ₂ Catalyst toward CO ₂ Methanation Wang, Fei; He, Shan; Chen, Hao Journal of the American Chemical Society, Vol. 138, Issue 19 https://doi.org/10.1021/jacs.6b02762	journal	May 2016
Tuning Selectivity of CO ₂ Hydrogenation Reactions at the Metal/Oxide Interface Kattel, Shyam; Liu, Ping; Chen, Jingguang G. Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b05362	journal	July 2017
Low-Temperature Restructuring of CeO ₂ -Supported Ru Nanoparticles Determines Selectivity in CO ₂ Catalytic Reduction Aitbekova, Aisulu; Wu, Liheng; Wrasman, Cody J. Journal of the American Chemical Society, Vol. 140, Issue 42 https://doi.org/10.1021/jacs.8b07615	journal	September 2018
Reticular Synthesis of Multinary Covalent Organic Frameworks Zhang, Bing; Mao, Haiyan; Matheu, Roc Journal of the American Chemical Society, Vol. 141, Issue 29 https://doi.org/10.1021/jacs.9b05626	journal	June 2019
Control of Molecular Bonding Strength on Metal Catalysts with Organic Monolayers for CO ₂ Reduction Zhang, Jing; Deo, Shyam; Janik, Michael J. Journal of the American Chemical Society, Vol. 142, Issue 11 https://doi.org/10.1021/jacs.9b12980	journal	February 2020
Statistical Methodology for the Detection of Small Changes in Distances by EXAFS: Application to the Antimalarial Ruthenoquine Curis, Emmanuel; Dubar, Faustine; Nicolis, Ioannis The Journal of Physical Chemistry A, Vol. 116, Issue 23 https://doi.org/10.1021/jp301811r	journal	May 2012
Activity Descriptors for CO ₂ Electroreduction to Methane on Transition-Metal Catalysts Peterson, Andrew A.; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201461p	journal	January 2012
Adsorbate-mediated strong metal–support interactions in oxide-supported Rh catalysts Matsubu, John C.; Zhang, Shuyi; DeRita, Leo Nature Chemistry, Vol. 9, Issue 2 https://doi.org/10.1038/nchem.2607	journal	September 2016
Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst Gao, Peng; Li, Shenggang; Bu, Xianni Nature Chemistry, Vol. 9, Issue 10 https://doi.org/10.1038/nchem.2794	journal	June 2017
Directly converting CO2 into a gasoline fuel Wei, Jian; Ge, Qingjie; Yao, Ruwei Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15174	journal	May 2017
Direct catalytic hydrogenation of CO2 to formate over a Schiff-base-mediated gold nanocatalyst Liu, Qinggang; Yang, Xiaofeng; Li, Lin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01673-3	journal	November 2017
CO2 hydrogenation to high-value products via heterogeneous catalysis Ye, Run-Ping; Ding, Jie; Gong, Weibo Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13638-9	journal	December 2019
Laminated self-standing covalent organic framework membrane with uniformly distributed subnanopores for ionic and molecular sieving Li, Yang; Wu, Qianxun; Guo, Xinghua Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-14056-7	journal	January 2020
Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction Zhu, Hong-Jing; Lu, Meng; Wang, Yi-Rong Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-019-14237-4	journal	January 2020
Tuning reactivity of Fischer–Tropsch synthesis by regulating TiOx overlayer over Ru/TiO2 nanocatalysts Zhang, Yaru; Yang, Xiaoli; Yang, Xiaofeng Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17044-4	journal	June 2020
Chemically stable polyarylether-based covalent organic frameworks Guan, Xinyu; Li, Hui; Ma, Yunchao Nature Chemistry, Vol. 11, Issue 6 https://doi.org/10.1038/s41557-019-0238-5	journal	April 2019
Covalent on-surface polymerization Grill, Leonhard; Hecht, Stefan Nature Chemistry, Vol. 12, Issue 2 https://doi.org/10.1038/s41557-019-0392-9	journal	January 2020
Higher CO2 concentrations increase extreme event risk in a 1.5 °C world Baker, Hugh S.; Millar, Richard J.; Karoly, David J. Nature Climate Change, Vol. 8, Issue 7 https://doi.org/10.1038/s41558-018-0190-1	journal	June 2018
Transition state and product diffusion control by polymer–nanocrystal hybrid catalysts Riscoe, Andrew R.; Wrasman, Cody J.; Herzing, Andrew A. Nature Catalysis, Vol. 2, Issue 10 https://doi.org/10.1038/s41929-019-0322-7	journal	August 2019
Strategies to break linear scaling relationships Pérez-Ramírez, Javier; López, Núria Nature Catalysis, Vol. 2, Issue 11 https://doi.org/10.1038/s41929-019-0376-6	journal	October 2019
Selective CO ₂ methanation on Ru/TiO ₂ catalysts: unravelling the decisive role of the TiO ₂ support crystal structure Kim, A.; Sanchez, C.; Patriarche, G. Catalysis Science & Technology, Vol. 6, Issue 22 https://doi.org/10.1039/C6CY01677D	journal	January 2016
A review of the catalytic hydrogenation of carbon dioxide into value-added hydrocarbons Yang, Haiyan; Zhang, Chen; Gao, Peng Catalysis Science & Technology, Vol. 7, Issue 20 https://doi.org/10.1039/C7CY01403A	journal	January 2017
New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO ₂ into hydrocarbon chemicals and fuels Zhou, Wei; Cheng, Kang; Kang, Jincan Chemical Society Reviews, Vol. 48, Issue 12 https://doi.org/10.1039/C8CS00502H	journal	January 2019
CO2 methanation property of Ru nanoparticle-loaded TiO2 prepared by a polygonal barrel-sputtering method Abe, Takayuki; Tanizawa, Masaaki; Watanabe, Kuniaki Energy & Environmental Science, Vol. 2, Issue 3 https://doi.org/10.1039/b817740f	journal	January 2009
Markedly Enhanced Surface Hydroxyl Groups of TiO2 Nanoparticles with Superior Water-Dispersibility for Photocatalysis Wu, Chung-Yi; Tu, Kuan-Ju; Deng, Jin-Pei Materials, Vol. 10, Issue 5 https://doi.org/10.3390/ma10050566	journal	May 2017

Similar Records

Steam-Assisted Selective CO₂ Hydrogenation to Ethanol over Ru–In Catalysts

Journal Article · 2024 · Angewandte Chemie (International Edition) · OSTI ID:2473047

Zhou, Chengshuang; Aitbekova, Aisulu; Liccardo, Gennaro; +13 more

Steam‐Assisted Selective CO ₂ Hydrogenation to Ethanol over Ru−In Catalysts

Journal Article · 2024 · Angewandte Chemie · OSTI ID:2530488

Zhou, Chengshuang; Aitbekova, Aisulu; Liccardo, Gennaro; +13 more

Steering CO ₂ electroreduction toward ethanol production by a surface-bound Ru polypyridyl carbene catalyst on N-doped porous carbon

Journal Article · 2019 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1577930

Liu, Yanming; Fan, Xinfei; Nayak, Animesh; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C-C coupling
CO2 hydrogenation
polymer/metal interface

Title: Steering CO 2 hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces

Citation Formats

References (53)

Similar Records

Related Subjects

Title: Steering CO ₂ hydrogenation toward C–C coupling to hydrocarbons using porous organic polymer/metal interfaces