The Predominance of Hydrogen Evolution on Transition Metal Sulfides and Phosphides under CO2 Reduction Conditions: An Experimental and Theoretical Study

Landers, Alan T.; Fields, Meredith; Torelli, Daniel A.; Xiao, Jianping; Hellstern, Thomas R.; Francis, Sonja A.; Tsai, Charlie; Kibsgaard, Jakob; Lewis, Nathan S.; Chan, Karen; Hahn, Christopher; Jaramillo, Thomas F.

doi:10.1021/acsenergylett.8b00237

Title: The Predominance of Hydrogen Evolution on Transition Metal Sulfides and Phosphides under CO₂ Reduction Conditions: An Experimental and Theoretical Study

Journal Article · Thu May 31 00:00:00 EDT 2018 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.8b00237· OSTI ID:1469213

Landers, Alan T. ^[1]; Fields, Meredith ^[2];

^[3];

^[2]; Hellstern, Thomas R. ^[2]; Francis, Sonja A. ^[3]; Tsai, Charlie ^[2];

^[4];

^[3];

^[2];

^[2]

Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
California Inst. of Technology (CalTech), Pasadena, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)

Here, a combination of experiment and theory has been used to understand the relationship between the hydrogen evolution reaction (HER) and CO₂ reduction (CO₂R) on transition metal phosphide and transition metal sulfide catalysts. Although multifunctional active sites in these materials could potentially improve their CO₂R activity relative to pure transition metal electrocatalysts, under aqueous testing conditions, these materials showed a high selectivity for the HER relative to CO₂R. Computational results supported these findings, indicating that a limitation of the metal phosphide catalysts is that the HER is favored thermodynamically over CO₂R. On Ni-MoS2, a limitation is the kinetic barrier for the proton–electron transfer to *CO. These theoretical and experimental results demonstrate that selective CO₂R requires electrocatalysts that possess both favorable thermodynamic pathways and surmountable kinetic barriers.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0004993

OSTI ID:: 1469213

Journal Information:: ACS Energy Letters, Vol. 3, Issue 6; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 54 works

Citation information provided by
Web of Science

References (51)

Prospects of CO₂ Utilization via Direct Heterogeneous Electrochemical Reduction Whipple, Devin T.; Kenis, Paul J. A. The Journal of Physical Chemistry Letters, Vol. 1, Issue 24, p. 3451-3458 https://doi.org/10.1021/jz1012627	journal	December 2010
Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide Kortlever, Ruud; Shen, Jing; Schouten, Klaas Jan P. The Journal of Physical Chemistry Letters, Vol. 6, Issue 20 https://doi.org/10.1021/acs.jpclett.5b01559	journal	September 2015
Opportunities and challenges in the electrocatalysis of CO2 and CO reduction using bifunctional surfaces: A theoretical and experimental study of Au–Cd alloys Jovanov, Zarko P.; Hansen, Heine A.; Varela, Ana Sofia Journal of Catalysis, Vol. 343 https://doi.org/10.1016/j.jcat.2016.04.008	journal	November 2016
Electrochemical CO₂ Reduction on Metal Electrodes Hori, Y.; Vayenas, Constantinos G.; White, Ralph E. Modern Aspects of Electrochemistry, p. 89-189 https://doi.org/10.1007/978-0-387-49489-0_3	book	January 2008
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
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Kuhl, Kendra P.; Cave, Etosha R.; Abram, David N. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21234j	journal	January 2012
Effects of electrolyte, catalyst, and membrane composition and operating conditions on the performance of solar-driven electrochemical reduction of carbon dioxide Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T. Physical Chemistry Chemical Physics, Vol. 17, Issue 29 https://doi.org/10.1039/C5CP03283K	journal	January 2015
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
Understanding trends in electrochemical carbon dioxide reduction rates Liu, Xinyan; Xiao, Jianping; Peng, Hongjie Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15438	journal	May 2017
Computational catalyst screening: Scaling, bond-order and catalysis Abild-Pedersen, Frank Catalysis Today, Vol. 272 https://doi.org/10.1016/j.cattod.2015.08.056	journal	September 2016
Materials for solar fuels and chemicals Montoya, Joseph H.; Seitz, Linsey C.; Chakthranont, Pongkarn Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4778	journal	December 2016
Bifunctional nature of a SiO2-supported Ni2P catalyst for hydrotreating: EXAFS and FTIR studies Lee, Y.; Oyama, S. Journal of Catalysis, Vol. 239, Issue 2 https://doi.org/10.1016/j.jcat.2005.12.029	journal	April 2006
Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces Fields, Meredith; Tsai, Charlie; Chen, Leanne D. ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.6b03403	journal	March 2017
Molybdenum Sulfides and Selenides as Possible Electrocatalysts for CO ₂ Reduction Chan, Karen; Tsai, Charlie; Hansen, Heine A. ChemCatChem, Vol. 6, Issue 7 https://doi.org/10.1002/cctc.201402128	journal	July 2014
How Doped MoS ₂ Breaks Transition-Metal Scaling Relations for CO ₂ Electrochemical Reduction Hong, Xin; Chan, Karen; Tsai, Charlie ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b00619	journal	June 2016
Robust carbon dioxide reduction on molybdenum disulphide edges Asadi, Mohammad; Kumar, Bijandra; Behranginia, Amirhossein Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5470	journal	July 2014
Nanostructured transition metal dichalcogenide electrocatalysts for CO ₂ reduction in ionic liquid Asadi, Mohammad; Kim, Kibum; Liu, Cong Science, Vol. 353, Issue 6298 https://doi.org/10.1126/science.aaf4767	journal	July 2016
Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide Abbasi, Pedram; Asadi, Mohammad; Liu, Cong ACS Nano, Vol. 11, Issue 1 https://doi.org/10.1021/acsnano.6b06392	journal	December 2016
Ionic Liquid-Mediated Selective Conversion of CO₂ to CO at Low Overpotentials Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R. Science, Vol. 334, Issue 6056, p. 643-644 https://doi.org/10.1126/science.1209786	journal	September 2011
In Situ Spectroscopic Examination of a Low Overpotential Pathway for Carbon Dioxide Conversion to Carbon Monoxide Rosen, Brian A.; Haan, John L.; Mukherjee, Prabuddha The Journal of Physical Chemistry C, Vol. 116, Issue 29, p. 15307-15312 https://doi.org/10.1021/jp210542v	journal	July 2012
Activation of CO ₂ by ionic liquid EMIM–BF ₄ in the electrochemical system: a theoretical study Wang, Yuanqing; Hatakeyama, Makoto; Ogata, Koji Physical Chemistry Chemical Physics, Vol. 17, Issue 36 https://doi.org/10.1039/C5CP02008E	journal	January 2015
MoP Nanoparticles Supported on Indium-Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO ₂ Electroreduction Sun, Xiaofu; Lu, Lu; Zhu, Qinggong Angewandte Chemie International Edition, Vol. 57, Issue 9 https://doi.org/10.1002/anie.201712221	journal	February 2018
Designing Active and Stable Silicon Photocathodes for Solar Hydrogen Production Using Molybdenum Sulfide Nanomaterials Benck, Jesse D.; Lee, Sang Chul; Fong, Kara D. Advanced Energy Materials, Vol. 4, Issue 18 https://doi.org/10.1002/aenm.201400739	journal	August 2014
Engineering Cobalt Phosphide (CoP) Thin Film Catalysts for Enhanced Hydrogen Evolution Activity on Silicon Photocathodes Hellstern, Thomas R.; Benck, Jesse D.; Kibsgaard, Jakob Advanced Energy Materials, Vol. 6, Issue 4 https://doi.org/10.1002/aenm.201501758	journal	December 2015
Low Temperature Solution-Phase Deposition of SnS Thin Films Antunez, Priscilla D.; Torelli, Daniel A.; Yang, Fan Chemistry of Materials, Vol. 26, Issue 19 https://doi.org/10.1021/cm503124u	journal	September 2014
Alkahest for V ₂ VI ₃ Chalcogenides: Dissolution of Nine Bulk Semiconductors in a Diamine-Dithiol Solvent Mixture Webber, David H.; Brutchey, Richard L. Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja4084336	journal	October 2013
Trioctylphosphine A General Phosphorus Source for the Low-Temperature Conversion of Metals into Metal Phosphides Henkes, Amanda E.; Schaak, Raymond E. Chemistry of Materials, Vol. 19, Issue 17, p. 4234-4242 https://doi.org/10.1021/cm071021w	journal	August 2007
Electrocatalytic and Photocatalytic Hydrogen Production from Acidic and Neutral-pH Aqueous Solutions Using Iron Phosphide Nanoparticles Callejas, Juan F.; McEnaney, Joshua M.; Read, Carlos G. ACS Nano, Vol. 8, Issue 11, p. 11101-11107 https://doi.org/10.1021/nn5048553	journal	October 2014
Synthesis, Characterization, and Properties of Metal Phosphide Catalysts for the Hydrogen-Evolution Reaction Callejas, Juan F.; Read, Carlos G.; Roske, Christopher W. Chemistry of Materials, Vol. 28, Issue 17 https://doi.org/10.1021/acs.chemmater.6b02148	journal	August 2016
Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao Nature Chemistry, Vol. 5, Issue 4 https://doi.org/10.1038/nchem.1574	journal	February 2013
Self-Supported Nanoporous Cobalt Phosphide Nanowire Arrays: An Efficient 3D Hydrogen-Evolving Cathode over the Wide Range of pH 0–14 Tian, Jingqi; Liu, Qian; Asiri, Abdullah M. Journal of the American Chemical Society, Vol. 136, Issue 21 https://doi.org/10.1021/ja503372r	journal	May 2014
Competition between Hydrogen Evolution and Carbon Dioxide Reduction on Copper Electrodes in Mildly Acidic Media Ooka, Hideshi; Figueiredo, Marta C.; Koper, Marc T. M. Langmuir, Vol. 33, Issue 37 https://doi.org/10.1021/acs.langmuir.7b00696	journal	May 2017
Effects of Anion Identity and Concentration on Electrochemical Reduction of CO ₂ Resasco, Joaquin; Lum, Yanwei; Clark, Ezra ChemElectroChem, Vol. 5, Issue 7 https://doi.org/10.1002/celc.201701316	journal	February 2018
Competition between CO ₂ Reduction and H ₂ Evolution on Transition-Metal Electrocatalysts Zhang, Yin-Jia; Sethuraman, Vijay; Michalsky, Ronald ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs5012298	journal	September 2014
Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces Shi, Chuan; Hansen, Heine A.; Lausche, Adam C. Physical Chemistry Chemical Physics, Vol. 16, Issue 10 https://doi.org/10.1039/c3cp54822h	journal	January 2014
Trends in the Catalytic Activity of Hydrogen Evolution during CO ₂ Electroreduction on Transition Metals Cave, Etosha R.; Shi, Chuan; Kuhl, Kendra P. ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b03807	journal	March 2018
Effects of adsorbed CO on the electrode reactions at a platinum electrode Kita, Hideaki; Ye, Shen; Sugimura, Kyoko Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 297, Issue 1 https://doi.org/10.1016/0022-0728(91)85374-X	journal	January 1991
Electrochemical Barriers Made Simple Chan, Karen; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 6, Issue 14 https://doi.org/10.1021/acs.jpclett.5b01043	journal	June 2015
Challenges in the first-principles description of reactions in electrocatalysis Schnur, Sebastian; Groß, Axel Catalysis Today, Vol. 165, Issue 1 https://doi.org/10.1016/j.cattod.2010.11.071	journal	May 2011
Nickel and cobalt phosphides as effective catalysts for oxygen removal of dibenzofuran: role of contact time, hydrogen pressure and hydrogen/feed molar ratio Infantes-Molina, A.; Gralberg, E.; Cecilia, J. A. Catalysis Science & Technology, Vol. 5, Issue 6 https://doi.org/10.1039/C5CY00282F	journal	January 2015
Universal transition state scaling relations for (de)hydrogenation over transition metals Wang, S.; Petzold, V.; Tripkovic, V. Physical Chemistry Chemical Physics, Vol. 13, Issue 46 https://doi.org/10.1039/c1cp20547a	journal	January 2011
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/c0ee00071j	journal	January 2010
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
Alloys of platinum and early transition metals as oxygen reduction electrocatalysts Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S. Nature Chemistry, Vol. 1, Issue 7, p. 552-556 https://doi.org/10.1038/nchem.367	journal	September 2009
Trends in the Exchange Current for Hydrogen Evolution Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of The Electrochemical Society, Vol. 152, Issue 3 https://doi.org/10.1149/1.1856988	journal	January 2005
Electrochemical Ammonia Synthesis—The Selectivity Challenge Singh, Aayush R.; Rohr, Brian A.; Schwalbe, Jay A. ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b03035	journal	December 2016
Potential Dependence of Electrochemical Barriers from ab Initio Calculations Chan, Karen; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acs.jpclett.6b00382	journal	April 2016
Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction Popczun, Eric J.; McKone, James R.; Read, Carlos G. Journal of the American Chemical Society, Vol. 135, Issue 25 https://doi.org/10.1021/ja403440e	journal	June 2013
Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water Bajdich, Michal; García-Mota, Mónica; Vojvodic, Aleksandra Journal of the American Chemical Society, Vol. 135, Issue 36 https://doi.org/10.1021/ja405997s	journal	August 2013
Application of Bravais-Friedel-Donnay-Harker, attachment energy and Ising models to predicting and understanding the morphology of molecular crystals Docherty, R.; Clydesdale, G.; Roberts, K. J. Journal of Physics D: Applied Physics, Vol. 24, Issue 2 https://doi.org/10.1088/0022-3727/24/2/001	journal	February 1991

Cited By (9)

Bi ₂ O ₃ Nanosheets Grown on Multi‐Channel Carbon Matrix to Catalyze Efficient CO ₂ Electroreduction to HCOOH Liu, Subiao; Lu, Xue Feng; Xiao, Jing Angewandte Chemie International Edition, Vol. 58, Issue 39 https://doi.org/10.1002/anie.201907674	journal	September 2019
Progress and Challenges Toward the Rational Design of Oxygen Electrocatalysts Based on a Descriptor Approach Liu, Jieyu; Liu, Hui; Chen, Haijun Advanced Science, Vol. 7, Issue 1 https://doi.org/10.1002/advs.201901614	journal	November 2019
Multifunctional Transition Metal‐Based Phosphides in Energy‐Related Electrocatalysis Li, Yang; Dong, Zihao; Jiao, Lifang Advanced Energy Materials, Vol. 10, Issue 11 https://doi.org/10.1002/aenm.201902104	journal	September 2019
Bi ₂ O ₃ Nanosheets Grown on Multi‐Channel Carbon Matrix to Catalyze Efficient CO ₂ Electroreduction to HCOOH Liu, Subiao; Lu, Xue Feng; Xiao, Jing Angewandte Chemie, Vol. 131, Issue 39 https://doi.org/10.1002/ange.201907674	journal	July 2019
Recent Progress on Titanium Dioxide Nanomaterials for Photocatalytic Applications Nasr, Maryline; Eid, Cynthia; Habchi, Roland ChemSusChem, Vol. 11, Issue 18 https://doi.org/10.1002/cssc.201800874	journal	August 2018
Robust and biocompatible catalysts for efficient hydrogen-driven microbial electrosynthesis Kracke, Frauke; Wong, Andrew Barnabas; Maegaard, Karen Communications Chemistry, Vol. 2, Issue 1 https://doi.org/10.1038/s42004-019-0145-0	journal	April 2019
Electrochemical Carbon Dioxide Splitting Xie, Jiafang; Huang, Yiyin; Wu, Maoxiang ChemElectroChem, Vol. 6, Issue 6 https://doi.org/10.1002/celc.201801716	journal	February 2019
Theoretical predication of the high hydrogen evolution catalytic activity for the cubic and tetragonal SnP systems Liu, Jingwei; Yu, Guangtao; Zhang, Ran Physical Chemistry Chemical Physics, Vol. 21, Issue 10 https://doi.org/10.1039/c9cp00618d	journal	January 2019
Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO ₂ by Molecular Catalysts Elouarzaki, Kamal; Kannan, Vishvak; Jose, Vishal Advanced Energy Materials, Vol. 9, Issue 24 https://doi.org/10.1002/aenm.201900090	journal	May 2019

Figures / Tables (5)

Similar Records

Active Role of Phosphorus in the Hydrogen Evolving Activity of Nickel Phosphide (0001) Surfaces

Journal Article · Mon Oct 02 00:00:00 EDT 2017 · ACS Catalysis · OSTI ID:1469213

Wexler, Robert B.; Martirez, John Mark P.; Rappe, Andrew M.

Selectivity for HCO₂^– over H₂ in the Electrochemical Catalytic Reduction of CO₂ by (POCOP)IrH₂

Journal Article · Mon Aug 15 00:00:00 EDT 2016 · ACS Catalysis · OSTI ID:1469213

Johnson, Samantha I.; Nielsen, Robert J.; Goddard, III, William A.

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

Journal Article · Mon Jan 15 00:00:00 EST 2018 · Advanced Materials · OSTI ID:1469213

Li, Hui; Li, Qi; Wen, Peng; +11 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: The Predominance of Hydrogen Evolution on Transition Metal Sulfides and Phosphides under CO2 Reduction Conditions: An Experimental and Theoretical Study

Citation Formats