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Title: Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof

Abstract

Catalysts prepared from abundant, cost effective metals, such as cobalt, nickel, chromium, manganese, iron, and copper, and containing one or more neutrally charged ligands (e.g., monodentate, bidentate, and/or polydentate ligands) and methods of making and using thereof are described herein. Exemplary ligands include, but are not limited to, phosphine ligands, nitrogen-based ligands, sulfur-based ligands, and/or arsenic-based ligands. In some embodiments, the catalyst is a cobalt-based catalyst or a nickel-based catalyst. The catalysts described herein are stable and active at neutral pH and in a wide range of buffers that are both weak and strong proton acceptors. While its activity is slightly lower than state of the art cobalt-based water oxidation catalysts under some conditions, it is capable of sustaining electrolysis at high applied potentials without a significant degradation in catalytic current. This enhanced robustness gives it an advantage in industrial and large-scale water electrolysis schemes.

Inventors:
; ; ; ;
Issue Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1484199
Patent Number(s):
10,081,650
Application Number:
14/322,773
Assignee:
Yale University (New Haven, CT)
DOE Contract Number:  
FG02-84ER13297
Resource Type:
Patent
Resource Relation:
Patent File Date: 2014 Jul 02
Country of Publication:
United States
Language:
English

Citation Formats

Bloomfield, Aaron J., Sheehan, Stafford W., Collom, Samuel L., Crabtree, Robert H., and Anastas, Paul T. Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof. United States: N. p., 2018. Web.
Bloomfield, Aaron J., Sheehan, Stafford W., Collom, Samuel L., Crabtree, Robert H., & Anastas, Paul T. Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof. United States.
Bloomfield, Aaron J., Sheehan, Stafford W., Collom, Samuel L., Crabtree, Robert H., and Anastas, Paul T. Tue . "Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof". United States. https://www.osti.gov/servlets/purl/1484199.
@article{osti_1484199,
title = {Metal oxide-organic hybrid materials for heterogeneous catalysis and methods of making and using thereof},
author = {Bloomfield, Aaron J. and Sheehan, Stafford W. and Collom, Samuel L. and Crabtree, Robert H. and Anastas, Paul T.},
abstractNote = {Catalysts prepared from abundant, cost effective metals, such as cobalt, nickel, chromium, manganese, iron, and copper, and containing one or more neutrally charged ligands (e.g., monodentate, bidentate, and/or polydentate ligands) and methods of making and using thereof are described herein. Exemplary ligands include, but are not limited to, phosphine ligands, nitrogen-based ligands, sulfur-based ligands, and/or arsenic-based ligands. In some embodiments, the catalyst is a cobalt-based catalyst or a nickel-based catalyst. The catalysts described herein are stable and active at neutral pH and in a wide range of buffers that are both weak and strong proton acceptors. While its activity is slightly lower than state of the art cobalt-based water oxidation catalysts under some conditions, it is capable of sustaining electrolysis at high applied potentials without a significant degradation in catalytic current. This enhanced robustness gives it an advantage in industrial and large-scale water electrolysis schemes.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {9}
}

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Works referenced in this record:

Reactions of dicyanodi-[1,2-bis(diphenylphosphino)ethane]cobalt(II) with oxygen and alkyl halides
journal, January 1970

  • Rigo, P.; Bressan, M.; Corain, B.
  • Journal of the Chemical Society D: Chemical Communications, Vol. 0, Issue 10, p. 598a
  • DOI: 10.1039/c2970000598a

Structure and Valency of a Cobalt−Phosphate Water Oxidation Catalyst Determined by in Situ X-ray Spectroscopy
journal, October 2010

  • Kanan, Matthew W.; Yano, Junko; Surendranath, Yogesh
  • Journal of the American Chemical Society, Vol. 132, Issue 39
  • DOI: 10.1021/ja1023767

Oxygen carrier and redox properties of some neutral cobalt chelates. Axial and in-plane ligand effects
journal, January 1974

  • Carter, Mark J.; Rillema, D. Paul; Basolo, Fred
  • Journal of the American Chemical Society, Vol. 96, Issue 2, p. 392-400
  • DOI: 10.1021/ja00809a012

Transition Metal−Boryl Compounds:  Synthesis, Reactivity, and Structure
journal, December 1998

  • Irvine, Geoffrey J.; Lesley, M. J. Gerald; Marder, Todd B.
  • Chemical Reviews, Vol. 98, Issue 8, p. 2685-2722
  • DOI: 10.1021/cr9500085

Elucidating the Domain Structure of the Cobalt Oxide Water Splitting Catalyst by X-ray Pair Distribution Function Analysis
journal, June 2012

  • Du, Pingwu; Kokhan, Oleksandr; Chapman, Karena W.
  • Journal of the American Chemical Society, Vol. 134, Issue 27
  • DOI: 10.1021/ja303826a

A oxygen-dependent reductive dechlorination of chloroform by (Bisdiphenylphosphinomethane)cobalthexacarbonyl Co2(CO)6(dppm)
journal, September 2006

  • Casadesus, Meritxell; Coogan, Michael P.; Oakley, Sarah
  • Journal of Organometallic Chemistry, Vol. 691, Issue 18, p. 3715-3717
  • DOI: 10.1016/j.jorganchem.2006.05.053

Hydroformylation of epoxides catalyzed by cobalt and hemilabile P–O ligands
journal, January 2000

  • Weber, R.; Keim, W.; Möthrath, M.
  • Chemical Communications, Vol. 0, Issue 15, p. 1419-1420
  • DOI: 10.1039/b002703k

Preparation and reactivity of new dioxygen adducts of rhodium containing phosphine ligands
journal, November 1986


Immobilizing catalysts on porous materials
journal, March 2006


Effects of Surface Anchoring Groups (Carboxylate vs Phosphonate) in Ruthenium-Complex-Sensitized TiO 2 on Visible Light Reactivity in Aqueous Suspensions
journal, September 2004

  • Bae, Eunyoung; Choi, Wonyong; Park, Jaiwook
  • The Journal of Physical Chemistry B, Vol. 108, Issue 37
  • DOI: 10.1021/jp047777p

Novel Binuclear Cobalt Dioxygen Complex—A Step on the Path to Dioxygen Activation
journal, October 1995

  • Reinaud, Olivia M.; Yap, Glenn P. A.; Rheingold, Arnold L.
  • Angewandte Chemie International Edition in English, Vol. 34, Issue 18, p. 2051-2052
  • DOI: 10.1002/anie.199520511

The reaction of Co4(CO)12 with Ph2PCH2CH2PPh2. Spectroscopic identification of polymeric products
journal, August 1986

  • Aime, Silvio; Gobetto, Roberto; Jannon, Giorgio
  • Journal of Organometallic Chemistry, Vol. 309, Issue 3, p. C51-C55
  • DOI: 10.1016/S0022-328X(00)99643-8

Material efficiency: rare and critical metals
journal, January 2013

  • Ayres, R. U.; Peiro, L. T.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 371, Issue 1986, p. 20110563-20110563
  • DOI: 10.1098/rsta.2011.0563

A heterogeneous water oxidation catalyst from dicobalt octacarbonyl and 1,2-bis(diphenylphosphino)ethane
journal, January 2014

  • Bloomfield, Aaron J.; Sheehan, Stafford W.; Collom, Samuel L.
  • New Journal of Chemistry, Vol. 38, Issue 4, p. 1540-1545
  • DOI: 10.1039/c3nj01298k

The Electrocatalysis of Oxygen Evolution on Perovskites
journal, January 1984

  • Bockris, John O'M.
  • Journal of The Electrochemical Society, Vol. 131, Issue 2
  • DOI: 10.1149/1.2115565

Electron transfer in organometallic clusters. 12. Regioselective sequential electrocatalytic substitution of [μ-(CF3)2C2]Co2(CO)6 by polydentate ligands
journal, July 1987

  • Cunninghame, Robert G.; Hanton, Lyall R.; Jensen, Simon D.
  • Organometallics, Vol. 6, Issue 7, p. 1470-1479
  • DOI: 10.1021/om00150a018

Nickel-borate oxygen-evolving catalyst that functions under benign conditions
journal, May 2010

  • Dinca, M.; Surendranath, Y.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 23
  • DOI: 10.1073/pnas.1001859107

Criticality of Non-Fuel Minerals: A Review of Major Approaches and Analyses
journal, September 2011

  • Erdmann, Lorenz; Graedel, Thomas E.
  • Environmental Science & Technology, Vol. 45, Issue 18
  • DOI: 10.1021/es200563g

The energy required to produce materials: constraints on energy-intensity improvements, parameters of demand
journal, March 2013

  • Gutowski, Timothy G.; Sahni, Sahil; Allwood, Julian M.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 371, Issue 1986
  • DOI: 10.1098/rsta.2012.0003

Precursor Transformation during Molecular Oxidation Catalysis with Organometallic Iridium Complexes
journal, July 2013

  • Hintermair, Ulrich; Sheehan, Stafford W.; Parent, Alexander R.
  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja4048762

EQCM Investigation of Electrochemical Deposition and Stability of Co–Pi Oxygen Evolution Catalyst of Solar Energy Storage
journal, April 2013

  • Irshad, Ahamed; Munichandraiah, Nookala
  • The Journal of Physical Chemistry C, Vol. 117, Issue 16, p. 8001-8008
  • DOI: 10.1021/jp312752q

Electrochemical and XPS investigations of cobalt in KOH solutions
journal, January 2000

  • Ismail, K. M.; Badawy, W. A.
  • Journal of Applied Electrochemistry, Vol. 30, Issue 11, p. 1303-1311
  • DOI: 10.1023/A:1026560422090

The anodic evolution of oxygen on Co3O4 film electrodes in alkaline solutions
journal, September 1981


In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+
journal, August 2008


Kinetics of Nucleation, Growth, and Stabilization of Cobalt Oxide Nanoclusters
journal, November 2003

  • King, S.; Hyunh, K.; Tannenbaum, R.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 44, p. 12097-12104
  • DOI: 10.1021/jp0355004

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

A Self-Healing Oxygen-Evolving Catalyst
journal, March 2009

  • Lutterman, Daniel A.; Surendranath, Yogesh; Nocera, Daniel G.
  • Journal of the American Chemical Society, Vol. 131, Issue 11
  • DOI: 10.1021/ja900023k

Metal Oxide Catalysts for the Evolution of O 2 from H 2 O
journal, March 2008

  • Merrill, Matthew D.; Dougherty, Ralph C.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 10
  • DOI: 10.1021/jp710675m

Chemical approaches to artificial photosynthesis
journal, May 1989


The Oxygen Electrode Reaction in Alkaline Solutions on Oxide Electrodes Prepared by the Thermal Decomposition Method
journal, January 1978

  • Miles, M. H.; Huang, Y. H.; Srinivasan, S.
  • Journal of The Electrochemical Society, Vol. 125, Issue 12, p. 1931-1934
  • DOI: 10.1149/1.2131330

The Artificial Leaf
journal, January 2012

  • Nocera, Daniel G.
  • Accounts of Chemical Research, Vol. 45, Issue 5
  • DOI: 10.1021/ar2003013

Fast and Persistent Electrocatalytic Water Oxidation by Co–Fe Prussian Blue Coordination Polymers
journal, August 2013

  • Pintado, Sara; Goberna-Ferrón, Sara; Escudero-Adán, Eduardo C.
  • Journal of the American Chemical Society, Vol. 135, Issue 36, p. 13270-13273
  • DOI: 10.1021/ja406242y

Combinatorial Search for Improved Metal Oxide Oxygen Evolution Electrocatalysts in Acidic Electrolytes
journal, January 2013

  • Seley, David; Ayers, Katherine; Parkinson, B. A.
  • ACS Combinatorial Science, Vol. 15, Issue 2
  • DOI: 10.1021/co300086h

Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis
journal, March 2013

  • Smith, Rodney D. L.; Prévot, Mathieu S.; Fagan, Randal D.
  • Science, Vol. 340, Issue 6128
  • DOI: 10.1126/science.1233638

Electrolyte-Dependent Electrosynthesis and Activity of Cobalt-Based Water Oxidation Catalysts
journal, February 2009

  • Surendranath, Yogesh; Dincǎ, Mircea; Nocera, Daniel G.
  • Journal of the American Chemical Society, Vol. 131, Issue 7
  • DOI: 10.1021/ja807769r

Nucleation, Growth, and Repair of a Cobalt-Based Oxygen Evolving Catalyst
journal, March 2012

  • Surendranath, Yogesh; Lutterman, Daniel A.; Liu, Yi
  • Journal of the American Chemical Society, Vol. 134, Issue 14
  • DOI: 10.1021/ja3000084

Characterization of cobalt oxides studied by FT-IR, Raman, TPR and TG-MS
journal, July 2008

  • Tang, Chih-Wei; Wang, Chen-Bin; Chien, Shu-Hua
  • Thermochimica Acta, Vol. 473, Issue 1-2, p. 68-73
  • DOI: 10.1016/j.tca.2008.04.015

Electrochemical Activation of Cp* Iridium Complexes for Electrode-Driven Water-Oxidation Catalysis
journal, September 2014

  • Thomsen, Julianne M.; Sheehan, Stafford W.; Hashmi, Sara M.
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja5068299

Self-Assembly of Active IrO 2 Colloid Catalyst on an ITO Electrode for Efficient Electrochemical Water Oxidation
journal, November 2005

  • Yagi, Masayuki; Tomita, Emi; Sakita, Sayaka
  • The Journal of Physical Chemistry B, Vol. 109, Issue 46
  • DOI: 10.1021/jp0550208

Electrosynthesis, functional, and structural characterization of a water-oxidizing manganese oxide
journal, January 2012

  • Zaharieva, Ivelina; Chernev, Petko; Risch, Marcel
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee21191b

Silica supported ruthenium oxide nanoparticulates as efficient catalysts for water oxidation
journal, January 2012

  • Zhang, Yang; Ren, Tong
  • Chemical Communications, Vol. 48, Issue 89, p. 11005-11007
  • DOI: 10.1039/c2cc35272a