Surface-Controlled TiO2 Nanocrystals with Catalytically Active Single-Site Co Incorporation for the Oxygen Evolution Reaction

Liu, Chang; Kwon, Soonho; Godbold, Perrin; Johnson, Grayson; Hwang, Sooyeon; Sun, Chengjun; Zhou, Hua; Goddard, William A.; Zhang, Sen

doi:10.1021/jacs.5c05795

Surface-Controlled TiO₂ Nanocrystals with Catalytically Active Single-Site Co Incorporation for the Oxygen Evolution Reaction

Journal Article · Tue May 27 00:00:00 EDT 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c05795· OSTI ID:2570592

^[1]; ^[2]; Godbold, Perrin ^[3]; ^[3]; ^[4]; Sun, Chengjun ^[5]; ^[5]; ^[2]; ^[3]

University of Virginia, Charlottesville, VA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
California Institute of Technology, Pasadena, CA (United States)
University of Virginia, Charlottesville, VA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

The design of advanced electrocatalysts is often hindered by uncertainties in identifying and controlling the active surfaces and catalytic centers within heterogeneous materials. Here we present the synthesis of single-site Co catalysts, substitutionally doped into surface-controlled TiO₂ anatase nanocrystals, aimed at enhancing the oxygen evolution reaction (OER). Grand canonical quantum mechanics calculations reveal that the kinetics of the OER, following an adsorbate evolution mechanism, is markedly influenced by the coordination environment of Co. The simulations suggest significantly higher turnover frequencies when Co is doped into the (001) surface of TiO₂ compared to the (101) surface. Consistent with the computational findings, experimental results show that Co-doped TiO₂ (Co-TiO₂) nanoplates with selectively exposed {001} surfaces exhibit enhanced current densities and turnover frequencies compared to Co-TiO₂ nanobipyramids with {101} surfaces. This study highlights the synergy between theoretical calculations and precision synthesis in the development of more effective catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Lab; Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 2570592

Alternate ID(s):: OSTI ID: 2570248

Report Number(s):: BNL-228321-2025-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 22 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (48)

Recent Progress in Low Pt Content Electrocatalysts for Hydrogen Evolution Reaction Li, Zheng; Ge, Ruixiang; Su, Jianwei Advanced Materials Interfaces, Vol. 7, Issue 14 https://doi.org/10.1002/admi.202000396	journal	May 2020
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico ChemCatChem, Vol. 3, Issue 7 https://doi.org/10.1002/cctc.201000397	journal	March 2011
Synthesis of High Metal Loading Single Atom Catalysts and Exploration of the Active Center Structure Wang, Kaiying; Wang, Xiaofeng; Liang, Xinhua ChemCatChem, Vol. 13, Issue 1 https://doi.org/10.1002/cctc.202001255	journal	November 2020
PtO_xCl_y(OH)_z(H₂O)_n Complexes under Oxidative and Reductive Conditions: Impact of the Level of Theory on Thermodynamic Stabilities Hellier, Adrien; Chizallet, Céline; Raybaud, Pascal ChemPhysChem, Vol. 24, Issue 3 https://doi.org/10.1002/cphc.202200711	journal	November 2022
Homogeneous versus Heterogeneous Catalysts in Water Oxidation: Homogeneous versus Heterogeneous Catalysts in Water Oxidation Fukuzumi, Shunichi; Hong, Dachao European Journal of Inorganic Chemistry, Vol. 2014, Issue 4 https://doi.org/10.1002/ejic.201300684	journal	August 2013
Electrolysis of water on oxide surfaces Rossmeisl, J.; Qu, Z. -W.; Zhu, H. Journal of Electroanalytical Chemistry, Vol. 607, Issue 1-2 https://doi.org/10.1016/j.jelechem.2006.11.008	journal	September 2007
Stabilizing alkaline fuel cells with a niobium-doped brookite titanium dioxide catalyst support Liu, Chang; Jung, Wonil; Jeon, Sungho Cell Reports Physical Science, Vol. 5, Issue 7 https://doi.org/10.1016/j.xcrp.2024.102090	journal	July 2024
Calculation of TiO ₂ Surface and Subsurface Oxygen Vacancy by the Screened Exchange Functional Li, Hongfei; Guo, Yuzheng; Robertson, John The Journal of Physical Chemistry C, Vol. 119, Issue 32 https://doi.org/10.1021/acs.jpcc.5b02430	journal	July 2015
Electrocatalytic Water Oxidation by a Trinuclear Copper(II) Complex Geer, Ana M.; Musgrave III, Charles; Webber, Christopher ACS Catalysis, Vol. 11, Issue 12 https://doi.org/10.1021/acscatal.1c01395	journal	June 2021
Immobilization of “Capping Arene” Cobalt(II) Complexes on Ordered Mesoporous Carbon for Electrocatalytic Water Oxidation Liu, Chang; Geer, Ana M.; Webber, Christopher ACS Catalysis, Vol. 11, Issue 24 https://doi.org/10.1021/acscatal.1c04617	journal	December 2021
Advances in Bridging Homogeneous and Heterogeneous Water Oxidation Catalysis by Insolubilized Polyoxometalate Clusters Hu, Qiyu; Zhou, Hongshan; Ding, Yong ACS Catalysis, Vol. 14, Issue 8 https://doi.org/10.1021/acscatal.4c00201	journal	April 2024
Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co ₃ O ₄ (001) Surface Pham, Hieu H.; Cheng, Mu-Jeng; Frei, Heinz ACS Catalysis, Vol. 6, Issue 8 https://doi.org/10.1021/acscatal.6b00713	journal	July 2016
Nonaqueous Synthesis of TiO ₂ Nanocrystals Using TiF ₄ to Engineer Morphology, Oxygen Vacancy Concentration, and Photocatalytic Activity Gordon, Thomas R.; Cargnello, Matteo; Paik, Taejong Journal of the American Chemical Society, Vol. 134, Issue 15 https://doi.org/10.1021/ja300823a	journal	April 2012
An Advanced Ni–Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation Gong, Ming; Li, Yanguang; Wang, Hailiang Journal of the American Chemical Society, Vol. 135, Issue 23 https://doi.org/10.1021/ja4027715	journal	May 2013
Water Oxidation Mechanism for Synthetic Co–Oxides with Small Nuclearity Li, Xichen; Siegbahn, Per E. M. Journal of the American Chemical Society, Vol. 135, Issue 37 https://doi.org/10.1021/ja4053448	journal	September 2013
CO₂ Reduction to Methane and Ethylene on a Single-Atom Catalyst: A Grand Canonical Quantum Mechanics Study Osella, Silvio; Goddard III, William A. Journal of the American Chemical Society, Vol. 145, Issue 39 https://doi.org/10.1021/jacs.3c05650	journal	September 2023
Facet-Dependent Oxygen Evolution Reaction Activity of IrO₂ from Quantum Mechanics and Experiments Kwon, Soonho; Stoerzinger, Kelsey A.; Rao, Reshma Journal of the American Chemical Society, Vol. 146, Issue 17 https://doi.org/10.1021/jacs.3c14271	journal	April 2024
Cobalt–Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and Composition on Activity, Stability, and Mechanism Burke, Michaela S.; Kast, Matthew G.; Trotochaud, Lena Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/jacs.5b00281	journal	March 2015
Structure Sensitivity of the Oxygen Evolution Reaction Catalyzed by Cobalt(II,III) Oxide Plaisance, Craig P.; van Santen, Rutger A. Journal of the American Chemical Society, Vol. 137, Issue 46 https://doi.org/10.1021/jacs.5b07779	journal	November 2015
Probing Edge Site Reactivity of Oxidic Cobalt Water Oxidation Catalysts Ullman, Andrew M.; Brodsky, Casey N.; Li, Nancy Journal of the American Chemical Society, Vol. 138, Issue 12 https://doi.org/10.1021/jacs.6b00762	journal	March 2016
The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO ₂ (110) Surface Ping, Yuan; Nielsen, Robert J.; Goddard, William A. Journal of the American Chemical Society, Vol. 139, Issue 1 https://doi.org/10.1021/jacs.6b07557	journal	December 2016
Reaction Mechanism for the Hydrogen Evolution Reaction on the Basal Plane Sulfur Vacancy Site of MoS ₂ Using Grand Canonical Potential Kinetics Huang, Yufeng; Nielsen, Robert J.; Goddard, William A. Journal of the American Chemical Society, Vol. 140, Issue 48 https://doi.org/10.1021/jacs.8b10016	journal	November 2018
Structure and Reactivity of Water Layers on Defect-Free and Defective Anatase TiO 2 (101) Surfaces Tilocca, Antonio; Selloni, Annabella The Journal of Physical Chemistry B, Vol. 108, Issue 15 https://doi.org/10.1021/jp037685k	journal	April 2004
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Interface Water on TiO ₂ Anatase (101) and (001) Surfaces: First-Principles Study with TiO ₂ Slabs Dipped in Bulk Water Sumita, Masato; Hu, Chunping; Tateyama, Yoshitaka The Journal of Physical Chemistry C, Vol. 114, Issue 43 https://doi.org/10.1021/jp105364z	journal	October 2010
Raman Spectroscopy: A New Approach to Measure the Percentage of Anatase TiO ₂ Exposed (001) Facets Tian, Fang; Zhang, Yupeng; Zhang, Jun The Journal of Physical Chemistry C, Vol. 116, Issue 13 https://doi.org/10.1021/jp301256h	journal	March 2012
Direct-Coupling O ₂ Bond Forming a Pathway in Cobalt Oxide Water Oxidation Catalysts Wang, Lee-Ping; Van Voorhis, Troy The Journal of Physical Chemistry Letters, Vol. 2, Issue 17 https://doi.org/10.1021/jz201021n	journal	August 2011
Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst Zhang, Miao; de Respinis, Moreno; Frei, Heinz Nature Chemistry, Vol. 6, Issue 4 https://doi.org/10.1038/nchem.1874	journal	February 2014
Reaction mechanism and kinetics for CO2 reduction on nickel single atom catalysts from quantum mechanics Hossain, Md Delowar; Huang, Yufeng; Yu, Ted H. Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16119-6	journal	May 2020
Potential-dependent transition of reaction mechanisms for oxygen evolution on layered double hydroxides Wang, Zeyu; Goddard, William A.; Xiao, Hai Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-40011-8	journal	July 2023
Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis Wu, Zhen-Yu; Chen, Feng-Yang; Li, Boyang Nature Materials, Vol. 22, Issue 1 https://doi.org/10.1038/s41563-022-01380-5	journal	October 2022
Nanoscale engineering of catalytic materials for sustainable technologies Mitchell, Sharon; Qin, Ruixuan; Zheng, Nanfeng Nature Nanotechnology, Vol. 16, Issue 2 https://doi.org/10.1038/s41565-020-00799-8	journal	November 2020
Electrified water treatment: fundamentals and roles of electrode materials Zuo, Kuichang; Garcia-Segura, Sergi; Cerrón-Calle, Gabriel A. Nature Reviews Materials, Vol. 8, Issue 7 https://doi.org/10.1038/s41578-023-00564-y	journal	May 2023
Key role of chemistry versus bias in electrocatalytic oxygen evolution Nong, Hong Nhan; Falling, Lorenz J.; Bergmann, Arno Nature, Vol. 587, Issue 7834 https://doi.org/10.1038/s41586-020-2908-2	journal	November 2020
Two-electron redox chemistry via single-atom catalyst for reversible zinc–air batteries Zhang, Wei; Zhang, Jiangwei; Wang, Nan Nature Sustainability, Vol. 7, Issue 4 https://doi.org/10.1038/s41893-024-01300-2	journal	February 2024
Impact of nanoparticle size and lattice oxygen on water oxidation on NiFeOxHy Roy, C.; Sebok, B.; Scott, S. B. Nature Catalysis, Vol. 1, Issue 11 https://doi.org/10.1038/s41929-018-0162-x	journal	November 2018
Iron-facilitated dynamic active-site generation on spinel CoAl2O4 with self-termination of surface reconstruction for water oxidation Wu, Tianze; Sun, Shengnan; Song, Jiajia Nature Catalysis, Vol. 2, Issue 9 https://doi.org/10.1038/s41929-019-0325-4	journal	August 2019
Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO2 nanorod surface Liu, Chang; Qian, Jin; Ye, Yifan Nature Catalysis, Vol. 4, Issue 1 https://doi.org/10.1038/s41929-020-00550-5	journal	December 2020
A strongly coupled Ru–CrOx cluster–cluster heterostructure for efficient alkaline hydrogen electrocatalysis Zhang, Bingxing; Wang, Jianmei; Liu, Guimei Nature Catalysis, Vol. 7, Issue 4 https://doi.org/10.1038/s41929-024-01126-3	journal	March 2024
Surface chemical state evaluation of CoSe₂ catalysts for the oxygen evolution reaction Zhang, Chengzhe; Tang, Bo; Gu, Xiaocong Chemical Communications, Vol. 55, Issue 73 https://doi.org/10.1039/C9CC05540A	journal	January 2019
Chlorine-doped α-Co(OH)₂ hollow nano-dodecahedrons prepared by a ZIF-67 self-sacrificing template route and enhanced OER catalytic activity Zha, Qingqing; Xu, Wenyan; Li, Xiaolei Dalton Transactions, Vol. 48, Issue 32 https://doi.org/10.1039/C9DT02141H	journal	January 2019
Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A. The Journal of Chemical Physics, Vol. 146, Issue 11 https://doi.org/10.1063/1.4978411	journal	March 2017
Structure and Energetics of Water Adsorbed at TiO 2 Anatase \(101\) and \(001\) Surfaces Vittadini, A.; Selloni, A.; Rotzinger, F. P. Physical Review Letters, Vol. 81, Issue 14 https://doi.org/10.1103/PhysRevLett.81.2954	journal	October 1998
Stress-Driven Reconstruction of an Oxide Surface: The Anatase TiO 2 ( 001 ) − ( 1 × 4 ) Surface Lazzeri, Michele; Selloni, Annabella Physical Review Letters, Vol. 87, Issue 26 https://doi.org/10.1103/PhysRevLett.87.266105	journal	December 2001
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles Suntivich, J.; May, K. J.; Gasteiger, H. A. Science, Vol. 334, Issue 6061 https://doi.org/10.1126/science.1212858	journal	October 2011
Homogeneously dispersed multimetal oxygen-evolving catalysts Zhang, B.; Zheng, X.; Voznyy, O. Science, Vol. 352, Issue 6283 https://doi.org/10.1126/science.aaf1525	journal	March 2016
A highly active and stable IrO _x /SrIrO ₃ catalyst for the oxygen evolution reaction Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori Science, Vol. 353, Issue 6303 https://doi.org/10.1126/science.aaf5050	journal	September 2016
Water-hydroxide trapping in cobalt tungstate for proton exchange membrane water electrolysis Ram, Ranit; Xia, Lu; Benzidi, Hind Science, Vol. 384, Issue 6702 https://doi.org/10.1126/science.adk9849	journal	June 2024

Figures / Tables (5)

Similar Records

Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO₂ nanorod surface

Journal Article · Sun Dec 13 19:00:00 EST 2020 · Nature Catalysis · OSTI ID:1760638

Related Subjects

25 ENERGY STORAGE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Catalysts
Nanocrystals
Nanoplates
Oxides
Radiology