Exploiting Metal–Ligand Cooperativity to Sequester, Activate, and Reduce Atmospheric Carbon Dioxide with a Neutral Zinc Complex

Cronin, Steve P.; Strain, Jacob M.; Mashuta, Mark S.; Spurgeon, Joshua M.; Buchanan, Robert M.; Grapperhaus, Craig A.

doi:10.1021/acs.inorgchem.0c00121

Exploiting Metal–Ligand Cooperativity to Sequester, Activate, and Reduce Atmospheric Carbon Dioxide with a Neutral Zinc Complex

Journal Article · Fri Mar 20 00:00:00 EDT 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.0c00121· OSTI ID:1800547

^[1]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]

Univ. of Louisville, KY (United States); OSTI
Univ. of Louisville, KY (United States)

As atmospheric levels of carbon dioxide (CO₂) continue to increase, there is an immediate need to balance the carbon cycle. Current approaches require multiple processes to fix CO₂ from the atmosphere or flue gas and then reduce it to value-added products. The zinc(II) catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) reduces CO₂ from air to formate with a faradaic efficiency of 15.1% based on total charge. The catalyst utilizes metal–ligand cooperativity and redox-active ligands to fix, activate, and reduce CO₂. Our approach provides a new strategy that incorporates sustainable earth-abundant metals that are oxygen and water tolerant.

View Accepted Manuscript (DOE)

Research Organization:: University of Louisville, KY (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-08CH11538

OSTI ID:: 1800547

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (39)

Metal-Ligand Cooperation Khusnutdinova, Julia R.; Milstein, David Angewandte Chemie International Edition, Vol. 54, Issue 42 https://doi.org/10.1002/anie.201503873	journal	September 2015
Local Proton Source in Electrocatalytic CO ₂ Reduction with [Mn(bpy-R)(CO) ₃ Br] Complexes Franco, Federico; Cometto, Claudio; Nencini, Luca Chemistry - A European Journal, Vol. 23, Issue 20 https://doi.org/10.1002/chem.201605546	journal	February 2017
A review of major non-power-related carbon dioxide stream compositions Last, George V.; Schmick, Mary T. Environmental Earth Sciences, Vol. 74, Issue 2 https://doi.org/10.1007/s12665-015-4105-4	journal	February 2015
Efficient electrocatalytic reduction of CO2 to CO on an electrodeposited Zn porous network Lu, Yu; Han, Bin; Tian, Chongchong Electrochemistry Communications, Vol. 97 https://doi.org/10.1016/j.elecom.2018.11.002	journal	December 2018
Properties of carbon dioxide absorption and reduction by sodium borohydride under atmospheric pressure Zhao, Yi; Zhang, Zili; Qian, Xinfeng Fuel, Vol. 142 https://doi.org/10.1016/j.fuel.2014.10.070	journal	February 2015
Complexes of group 12 metals containing a hybrid thiosemicarbazone-pyridylhydrazone ligand Calatayud, David G.; López-Torres, Elena; Dilworth, Jonathan R. Inorganica Chimica Acta, Vol. 381 https://doi.org/10.1016/j.ica.2011.10.023	journal	February 2012
An overview of current status of carbon dioxide capture and storage technologies Leung, Dennis Y. C.; Caramanna, Giorgio; Maroto-Valer, M. Mercedes Renewable and Sustainable Energy Reviews, Vol. 39 https://doi.org/10.1016/j.rser.2014.07.093	journal	November 2014
A systematic review on CO2 capture with ionic liquids: Current status and future prospects Aghaie, Mahsa; Rezaei, Nima; Zendehboudi, Sohrab Renewable and Sustainable Energy Reviews, Vol. 96 https://doi.org/10.1016/j.rser.2018.07.004	journal	November 2018
Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts Francke, Robert; Schille, Benjamin; Roemelt, Michael Chemical Reviews, Vol. 118, Issue 9 https://doi.org/10.1021/acs.chemrev.7b00459	journal	January 2018
Metal-Assisted Ligand-Centered Electrocatalytic Hydrogen Evolution upon Reduction of a Bis(thiosemicarbazonato)Cu(II) Complex Haddad, Andrew Z.; Cronin, Steve P.; Mashuta, Mark S. Inorganic Chemistry, Vol. 56, Issue 18 https://doi.org/10.1021/acs.inorgchem.7b01608	journal	August 2017
Electrocatalytic Reduction of CO ₂ to Formate by an Iron Schiff Base Complex Nichols, Asa W.; Chatterjee, Sayanti; Sabat, Michal Inorganic Chemistry, Vol. 57, Issue 4 https://doi.org/10.1021/acs.inorgchem.7b02955	journal	January 2018
Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst Cronin, Steve P.; Mamun, Abdullah Al; Toda, Megan J. Inorganic Chemistry, Vol. 58, Issue 19 https://doi.org/10.1021/acs.inorgchem.9b01912	journal	September 2019
An Iron Electrocatalyst for Selective Reduction of CO ₂ to Formate in Water: Including Thermochemical Insights Taheri, Atefeh; Thompson, Emily J.; Fettinger, James C. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b01708	journal	November 2015
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO ₂ Fixation Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B. Chemical Reviews, Vol. 113, Issue 8 https://doi.org/10.1021/cr300463y	journal	June 2013
Facile carbon dioxide uptake by zinc(II)-tetraazacycloalkane complexes. 1. Syntheses, characterizations, and chemical properties of (monoalkyl carbonato)(tetraazacycloalkane)zinc(II) complexes Kato, Masako; Ito, Tasuku Inorganic Chemistry, Vol. 24, Issue 4 https://doi.org/10.1021/ic00198a015	journal	February 1985
Facile carbon dioxide uptake by zinc(II)-tetraazacycloalkane complexes. 2. X-ray structural studies of (.mu.-monomethyl carbonato)(1,4,8,11-tetraazacyclotetradecane)zinc(II) perchlorate, bis(.mu.-monomethyl carbonato)tris[(1,4,8,12-tetraazacyclopentadecane)zinc(II)] perchlorate, and (monomethyl carbonato)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)zinc(II) perchlorate Kato, Masako; Ito, Tasuku Inorganic Chemistry, Vol. 24, Issue 4 https://doi.org/10.1021/ic00198a016	journal	February 1985
Copper Complexes of Thiosemicarbazone−Pyridylhydrazine (THYNIC) Hybrid Ligands: A New Versatile Potential Bifunctional Chelator for Copper Radiopharmaceuticals Cowley, Andrew R.; Dilworth, Jonathan R.; Donnelly, Paul S. Inorganic Chemistry, Vol. 45, Issue 2 https://doi.org/10.1021/ic0514492	journal	January 2006
H ₂ Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation Fourmond, Vincent; Jacques, Pierre-André; Fontecave, Marc Inorganic Chemistry, Vol. 49, Issue 22 https://doi.org/10.1021/ic101187v	journal	November 2010
Single-Site β-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO ₂ and Epoxides: Catalyst Synthesis and Unprecedented Polymerization Activity Cheng, Ming; Moore, David R.; Reczek, Joseph J. Journal of the American Chemical Society, Vol. 123, Issue 36 https://doi.org/10.1021/ja003850n	journal	September 2001
Using a One-Electron Shuttle for the Multielectron Reduction of CO₂ to Methanol: Kinetic, Mechanistic, and Structural Insights Barton Cole, Emily; Lakkaraju, Prasad S.; Rampulla, David M. Journal of the American Chemical Society, Vol. 132, Issue 33, p. 11539-11551 https://doi.org/10.1021/ja1023496	journal	August 2010
Electrochemistry of Acids on Platinum. Application to the Reduction of Carbon Dioxide in the Presence of Pyridinium Ion in Water Costentin, Cyrille; Canales, Juan Carlos; Haddou, Baptiste Journal of the American Chemical Society, Vol. 135, Issue 47 https://doi.org/10.1021/ja407988w	journal	November 2013
CO ₂ Capture by a Rhenium(I) Complex with the Aid of Triethanolamine Morimoto, Tatsuki; Nakajima, Takuya; Sawa, Shuhei Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja409271s	journal	October 2013
Manganese Catalysts with Bulky Bipyridine Ligands for the Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization and Altering Catalysis Sampson, Matthew D.; Nguyen, An D.; Grice, Kyle A. Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja501252f	journal	February 2014
Metal–Organic Frameworks for Electrocatalytic Reduction of Carbon Dioxide Kornienko, Nikolay; Zhao, Yingbo; Kley, Christopher S. Journal of the American Chemical Society, Vol. 137, Issue 44 https://doi.org/10.1021/jacs.5b08212	journal	October 2015
Beyond Metal-Hydrides: Non-Transition-Metal and Metal-Free Ligand-Centered Electrocatalytic Hydrogen Evolution and Hydrogen Oxidation Haddad, Andrew Z.; Garabato, Brady D.; Kozlowski, Pawel M. Journal of the American Chemical Society, Vol. 138, Issue 25 https://doi.org/10.1021/jacs.6b04441	journal	June 2016
Turning on the Protonation-First Pathway for Electrocatalytic CO ₂ Reduction by Manganese Bipyridyl Tricarbonyl Complexes Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b08776	journal	February 2017
Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid Roy, Souvik; Sharma, Bhaskar; Pécaut, Jacques Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.6b11474	journal	March 2017
Reaction of electrophiles with manganese(I) and rhenium(I) alkoxide complexes: reversible absorption of atmospheric carbon dioxide Mandal, Santosh K.; Ho, Douglas M.; Orchin, Milton Organometallics, Vol. 12, Issue 5 https://doi.org/10.1021/om00029a032	journal	May 1993
The chemistry of metal–organic frameworks for CO2 capture, regeneration and conversion Trickett, Christopher A.; Helal, Aasif; Al-Maythalony, Bassem A. Nature Reviews Materials, Vol. 2, Issue 8 https://doi.org/10.1038/natrevmats.2017.45	journal	July 2017
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels Qiao, Jinli; Liu, Yuyu; Hong, Feng Chem. Soc. Rev., Vol. 43, Issue 2 https://doi.org/10.1039/C3CS60323G	journal	January 2014
Fixation of atmospheric carbon dioxide by ruthenium complexes bearing an NHC-based pincer ligand: formation of a methylcarbonato complex and its methylation Arikawa, Yasuhiro; Nakamura, Takuo; Ogushi, Shinji Dalton Transactions, Vol. 44, Issue 12 https://doi.org/10.1039/C5DT00476D	journal	January 2015
Progress in catalyst exploration for heterogeneous CO ₂ reduction and utilization: a critical review Zhao, Guixia; Huang, Xiubing; Wang, Xiangxue J. Mater. Chem. A, Vol. 5, Issue 41 https://doi.org/10.1039/C7TA07290B	journal	January 2017
Electrocatalytic reduction of low concentration CO ₂ Kumagai, Hiromu; Nishikawa, Tetsuya; Koizumi, Hiroki Chemical Science, Vol. 10, Issue 6 https://doi.org/10.1039/C8SC04124E	journal	January 2019
A look at periodic trends in d-block molecular electrocatalysts for CO ₂ reduction Jiang, Changcheng; Nichols, Asa W.; Machan, Charles W. Dalton Transactions, Vol. 48, Issue 26 https://doi.org/10.1039/C9DT00491B	journal	January 2019
Catalysts for CO ₂ /epoxide ring-opening copolymerization Trott, G.; Saini, P. K.; Williams, C. K. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 374, Issue 2061 https://doi.org/10.1098/rsta.2015.0085	journal	February 2016
ORTEP -3 for Windows - a version of ORTEP -III with a Graphical User Interface (GUI) Farrugia, L. J. Journal of Applied Crystallography, Vol. 30, Issue 5 https://doi.org/10.1107/S0021889897003117	journal	October 1997
High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO₂ Capture Banerjee, Rahul; Phan, Anh; Wang, Bo Science, Vol. 319, Issue 5865, p. 939-943 https://doi.org/10.1126/science.1152516	journal	February 2008
New climate models forecast a warming surge Voosen, Paul Science, Vol. 364, Issue 6437 https://doi.org/10.1126/science.364.6437.222	journal	April 2019
The broadening reach of frustrated Lewis pair chemistry Stephan, D. W. Science, Vol. 354, Issue 6317 https://doi.org/10.1126/science.aaf7229	journal	December 2016

Similar Records

Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst

Journal Article · Mon Sep 09 20:00:00 EDT 2019 · Inorganic Chemistry · OSTI ID:1800549

Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates

Journal Article · Mon May 21 20:00:00 EDT 2018 · Journal of Physical Chemistry Letters · OSTI ID:1467603

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Alcohols
Atmospheric chemistry
Chemistry
Electrodes
Inorganic carbon compounds
Oxides

Exploiting Metal–Ligand Cooperativity to Sequester, Activate, and Reduce Atmospheric Carbon Dioxide with a Neutral Zinc Complex

Citation Formats

References (39)

Linked Research (1)

Similar Records

Related Subjects