Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2

Selective reduction of CO2 to formate represents an ongoing challenge in photoelectrocatalysis. To provide mechanistic insights, we investigate the kinetics of hydride transfer (HT) from a series of metal-free hydride donors to CO2. The observed dependence of experimental and calculated HT barriers...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry letters 2021-03, Vol.12 (9), p.2306-2311
Main Authors: Weerasooriya, Ravindra B, Gesiorski, Jonathan L, Alherz, Abdulaziz, Ilic, Stefan, Hargenrader, George N, Musgrave, Charles B, Glusac, Ksenija D
Format: Article
Language:English
Subjects:
CO2 reduction, organo-hydrides, Marcus theory, product selectivity, hydride transfer, formate
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Physical Insights into Chemistry, Catalysis, and Interfaces
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by
cites
container_end_page 2311
container_issue 9
container_start_page 2306
container_title The journal of physical chemistry letters
container_volume 12
creator Weerasooriya, Ravindra B
Gesiorski, Jonathan L
Alherz, Abdulaziz
Ilic, Stefan
Hargenrader, George N
Musgrave, Charles B
Glusac, Ksenija D
description Selective reduction of CO2 to formate represents an ongoing challenge in photoelectrocatalysis. To provide mechanistic insights, we investigate the kinetics of hydride transfer (HT) from a series of metal-free hydride donors to CO2. The observed dependence of experimental and calculated HT barriers on the thermodynamic driving force was modeled by using the Marcus hydride transfer formalism to obtain the insights into the effect of reorganization energies on the reaction kinetics. Our results indicate that even if the most ideal hydride donor were discovered, the HT to CO2 would exhibit sluggish kinetics (
doi_str_mv 10.1021/acs.jpclett.0c03662
format article
fullrecord <record><control><sourceid>proquest_osti_</sourceid><recordid>TN_cdi_osti_scitechconnect_1798205</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2496252758</sourcerecordid><originalsourceid>FETCH-LOGICAL-a366t-3161054cdd063ffa428892f175a5686476cf1e2d89f9a045e5dd16abb8af9a2a3</originalsourceid><addsrcrecordid>eNpNkLFOwzAURS0EEqXwBSwWE0ta24kdZ0SBUkRRlzJbrvMsUqV2sd2Bv8eQCjG9q6ujp6uD0C0lM0oYnWsTZ7uDGSClGTGkFIKdoQltKlnUVPLzf_kSXcW4I0Q0RNYTtHrtHaTeROwtXn51oe8Ab4J20ULANvg9bnXSw1dm8BvkVCwCwB_66J0PESeP2zW7RhdWDxFuTneK3hdPm3ZZrNbPL-3DqtB5WSpKKijhlek6IkprdcWkbJilNddcSFHVwlgKrJONbTSpOPCuo0Jvt1Lngulyiu7Gvz6mXkXTJzAfxjsHJilaN5IRnqH7EToE_3mEmNS-jwaGQTvwx6hY1QjGWc1lRucjmj2qnT8Gl9crStSPXPVbjnLVSW75DQhQbtU</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2496252758</pqid></control><display><type>article</type><title>Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Weerasooriya, Ravindra B ; Gesiorski, Jonathan L ; Alherz, Abdulaziz ; Ilic, Stefan ; Hargenrader, George N ; Musgrave, Charles B ; Glusac, Ksenija D</creator><creatorcontrib>Weerasooriya, Ravindra B ; Gesiorski, Jonathan L ; Alherz, Abdulaziz ; Ilic, Stefan ; Hargenrader, George N ; Musgrave, Charles B ; Glusac, Ksenija D ; Argonne National Lab. (ANL), Argonne, IL (United States)</creatorcontrib><description>Selective reduction of CO2 to formate represents an ongoing challenge in photoelectrocatalysis. To provide mechanistic insights, we investigate the kinetics of hydride transfer (HT) from a series of metal-free hydride donors to CO2. The observed dependence of experimental and calculated HT barriers on the thermodynamic driving force was modeled by using the Marcus hydride transfer formalism to obtain the insights into the effect of reorganization energies on the reaction kinetics. Our results indicate that even if the most ideal hydride donor were discovered, the HT to CO2 would exhibit sluggish kinetics (&lt;100 turnovers per second at −0.1 eV driving force), indicating that the conventional HT may not be an appropriate mechanism for solar conversion of CO2 to formate. We propose that the conventional HT mechanism should not be considered for CO2 reduction catalysis and argue that the orthogonal HT mechanism, previously proposed to address thermodynamic limitations of this reaction, may also lead to lower kinetic barriers for CO2 reduction to formate.</description><identifier>ISSN: 1948-7185</identifier><identifier>EISSN: 1948-7185</identifier><identifier>DOI: 10.1021/acs.jpclett.0c03662</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>CO2 reduction, organo-hydrides, Marcus theory, product selectivity, hydride transfer, formate ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; Physical Insights into Chemistry, Catalysis, and Interfaces</subject><ispartof>The journal of physical chemistry letters, 2021-03, Vol.12 (9), p.2306-2311</ispartof><rights>2021 American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0002-2734-057X ; 0000-0002-5732-3180 ; 0000-0002-6305-4001 ; 0000-0001-7529-3483 ; 0000000257323180 ; 0000000175293483 ; 000000022734057X ; 0000000263054001</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,27924,27925</link.rule.ids><backlink>$$Uhttps://www.osti.gov/servlets/purl/1798205$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Weerasooriya, Ravindra B</creatorcontrib><creatorcontrib>Gesiorski, Jonathan L</creatorcontrib><creatorcontrib>Alherz, Abdulaziz</creatorcontrib><creatorcontrib>Ilic, Stefan</creatorcontrib><creatorcontrib>Hargenrader, George N</creatorcontrib><creatorcontrib>Musgrave, Charles B</creatorcontrib><creatorcontrib>Glusac, Ksenija D</creatorcontrib><creatorcontrib>Argonne National Lab. (ANL), Argonne, IL (United States)</creatorcontrib><title>Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2</title><title>The journal of physical chemistry letters</title><addtitle>J. Phys. Chem. Lett</addtitle><description>Selective reduction of CO2 to formate represents an ongoing challenge in photoelectrocatalysis. To provide mechanistic insights, we investigate the kinetics of hydride transfer (HT) from a series of metal-free hydride donors to CO2. The observed dependence of experimental and calculated HT barriers on the thermodynamic driving force was modeled by using the Marcus hydride transfer formalism to obtain the insights into the effect of reorganization energies on the reaction kinetics. Our results indicate that even if the most ideal hydride donor were discovered, the HT to CO2 would exhibit sluggish kinetics (&lt;100 turnovers per second at −0.1 eV driving force), indicating that the conventional HT may not be an appropriate mechanism for solar conversion of CO2 to formate. We propose that the conventional HT mechanism should not be considered for CO2 reduction catalysis and argue that the orthogonal HT mechanism, previously proposed to address thermodynamic limitations of this reaction, may also lead to lower kinetic barriers for CO2 reduction to formate.</description><subject>CO2 reduction, organo-hydrides, Marcus theory, product selectivity, hydride transfer, formate</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>Physical Insights into Chemistry, Catalysis, and Interfaces</subject><issn>1948-7185</issn><issn>1948-7185</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpNkLFOwzAURS0EEqXwBSwWE0ta24kdZ0SBUkRRlzJbrvMsUqV2sd2Bv8eQCjG9q6ujp6uD0C0lM0oYnWsTZ7uDGSClGTGkFIKdoQltKlnUVPLzf_kSXcW4I0Q0RNYTtHrtHaTeROwtXn51oe8Ab4J20ULANvg9bnXSw1dm8BvkVCwCwB_66J0PESeP2zW7RhdWDxFuTneK3hdPm3ZZrNbPL-3DqtB5WSpKKijhlek6IkprdcWkbJilNddcSFHVwlgKrJONbTSpOPCuo0Jvt1Lngulyiu7Gvz6mXkXTJzAfxjsHJilaN5IRnqH7EToE_3mEmNS-jwaGQTvwx6hY1QjGWc1lRucjmj2qnT8Gl9crStSPXPVbjnLVSW75DQhQbtU</recordid><startdate>20210311</startdate><enddate>20210311</enddate><creator>Weerasooriya, Ravindra B</creator><creator>Gesiorski, Jonathan L</creator><creator>Alherz, Abdulaziz</creator><creator>Ilic, Stefan</creator><creator>Hargenrader, George N</creator><creator>Musgrave, Charles B</creator><creator>Glusac, Ksenija D</creator><general>American Chemical Society</general><scope>7X8</scope><scope>OIOZB</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0002-2734-057X</orcidid><orcidid>https://orcid.org/0000-0002-5732-3180</orcidid><orcidid>https://orcid.org/0000-0002-6305-4001</orcidid><orcidid>https://orcid.org/0000-0001-7529-3483</orcidid><orcidid>https://orcid.org/0000000257323180</orcidid><orcidid>https://orcid.org/0000000175293483</orcidid><orcidid>https://orcid.org/000000022734057X</orcidid><orcidid>https://orcid.org/0000000263054001</orcidid></search><sort><creationdate>20210311</creationdate><title>Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2</title><author>Weerasooriya, Ravindra B ; Gesiorski, Jonathan L ; Alherz, Abdulaziz ; Ilic, Stefan ; Hargenrader, George N ; Musgrave, Charles B ; Glusac, Ksenija D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a366t-3161054cdd063ffa428892f175a5686476cf1e2d89f9a045e5dd16abb8af9a2a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>CO2 reduction, organo-hydrides, Marcus theory, product selectivity, hydride transfer, formate</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>Physical Insights into Chemistry, Catalysis, and Interfaces</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Weerasooriya, Ravindra B</creatorcontrib><creatorcontrib>Gesiorski, Jonathan L</creatorcontrib><creatorcontrib>Alherz, Abdulaziz</creatorcontrib><creatorcontrib>Ilic, Stefan</creatorcontrib><creatorcontrib>Hargenrader, George N</creatorcontrib><creatorcontrib>Musgrave, Charles B</creatorcontrib><creatorcontrib>Glusac, Ksenija D</creatorcontrib><creatorcontrib>Argonne National Lab. (ANL), Argonne, IL (United States)</creatorcontrib><collection>MEDLINE - Academic</collection><collection>OSTI.GOV - Hybrid</collection><collection>OSTI.GOV</collection><jtitle>The journal of physical chemistry letters</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Weerasooriya, Ravindra B</au><au>Gesiorski, Jonathan L</au><au>Alherz, Abdulaziz</au><au>Ilic, Stefan</au><au>Hargenrader, George N</au><au>Musgrave, Charles B</au><au>Glusac, Ksenija D</au><aucorp>Argonne National Lab. (ANL), Argonne, IL (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2</atitle><jtitle>The journal of physical chemistry letters</jtitle><addtitle>J. Phys. Chem. Lett</addtitle><date>2021-03-11</date><risdate>2021</risdate><volume>12</volume><issue>9</issue><spage>2306</spage><epage>2311</epage><pages>2306-2311</pages><issn>1948-7185</issn><eissn>1948-7185</eissn><abstract>Selective reduction of CO2 to formate represents an ongoing challenge in photoelectrocatalysis. To provide mechanistic insights, we investigate the kinetics of hydride transfer (HT) from a series of metal-free hydride donors to CO2. The observed dependence of experimental and calculated HT barriers on the thermodynamic driving force was modeled by using the Marcus hydride transfer formalism to obtain the insights into the effect of reorganization energies on the reaction kinetics. Our results indicate that even if the most ideal hydride donor were discovered, the HT to CO2 would exhibit sluggish kinetics (&lt;100 turnovers per second at −0.1 eV driving force), indicating that the conventional HT may not be an appropriate mechanism for solar conversion of CO2 to formate. We propose that the conventional HT mechanism should not be considered for CO2 reduction catalysis and argue that the orthogonal HT mechanism, previously proposed to address thermodynamic limitations of this reaction, may also lead to lower kinetic barriers for CO2 reduction to formate.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/acs.jpclett.0c03662</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-2734-057X</orcidid><orcidid>https://orcid.org/0000-0002-5732-3180</orcidid><orcidid>https://orcid.org/0000-0002-6305-4001</orcidid><orcidid>https://orcid.org/0000-0001-7529-3483</orcidid><orcidid>https://orcid.org/0000000257323180</orcidid><orcidid>https://orcid.org/0000000175293483</orcidid><orcidid>https://orcid.org/000000022734057X</orcidid><orcidid>https://orcid.org/0000000263054001</orcidid><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 1948-7185
ispartof The journal of physical chemistry letters, 2021-03, Vol.12 (9), p.2306-2311
issn 1948-7185
1948-7185
language eng
recordid cdi_osti_scitechconnect_1798205
source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
subjects CO2 reduction, organo-hydrides, Marcus theory, product selectivity, hydride transfer, formate
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Physical Insights into Chemistry, Catalysis, and Interfaces
title Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-05T08%3A50%3A00IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_osti_&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Kinetics%20of%20Hydride%20Transfer%20from%20Catalytic%20Metal-Free%20Hydride%20Donors%20to%20CO2&rft.jtitle=The%20journal%20of%20physical%20chemistry%20letters&rft.au=Weerasooriya,%20Ravindra%20B&rft.aucorp=Argonne%20National%20Lab.%20(ANL),%20Argonne,%20IL%20(United%20States)&rft.date=2021-03-11&rft.volume=12&rft.issue=9&rft.spage=2306&rft.epage=2311&rft.pages=2306-2311&rft.issn=1948-7185&rft.eissn=1948-7185&rft_id=info:doi/10.1021/acs.jpclett.0c03662&rft_dat=%3Cproquest_osti_%3E2496252758%3C/proquest_osti_%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a366t-3161054cdd063ffa428892f175a5686476cf1e2d89f9a045e5dd16abb8af9a2a3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=2496252758&rft_id=info:pmid/&rfr_iscdi=true