Ligand removal energetics control CO2 electroreduction selectivity on atomically precise, ligated alloy nanoclusters

Rybacki, Malena; Nagarajan, Anantha Venkataraman; Mpourmpakis, Giannis

doi:10.1039/d2en00157h

Ligand removal energetics control CO₂ electroreduction selectivity on atomically precise, ligated alloy nanoclusters

Journal Article · Fri Apr 29 00:00:00 EDT 2022 · Environmental Science: Nano

DOI:https://doi.org/10.1039/d2en00157h· OSTI ID:1982249

Rybacki, Malena ^[1]; ^[1]; ^[1]

Univ. of Pittsburgh, PA (United States)

Atomically precise, thiolate-protected gold nanoclusters (TPNCs) exhibit remarkable catalytic performance for the electrochemical reduction of carbon dioxide (CO₂R) to CO. The origin of their high CO₂R activity and selectivity has been attributed to partial ligand removal from the thiolate-covered surfaces of TPNCs to expose catalytically active sulfur atoms. Recently, heterometal doped (alloy) TPNCs have been shown to exhibit enhanced CO₂R activity and selectivity compared to their monometallic counterparts. However, systematic studies on the effect of doping (metal type and location on TPNC) on active site exposure and CO₂R activity are missing in literature. Herein, we apply Density Functional Theory calculations to investigate the effect of heterometal (Pt, Pd, Hg and Cd) doping of Au₂₅(SR)₁₈ TPNC on the active site exposure and CO₂R activity and selectivity. In this study, we reveal that doping significantly modifies relevant TPNC electronic properties, such as electron affinity, while also altering partial ligand removal and carboxyl (*COOH) intermediate formation energies. Furthermore, we demonstrate that changing the dopant (e.g. Hg) position can change the selectivity of the TPNC towards CO_(g) or H_2(g) formation, highlighting the importance of dopant locations in TPNC-based CO₂R. Most notably, we report a universal (i.e. capturing different dopant types and positions) linear trend between the ligand removal energy and i) the *COOH formation energy, as well as, ii) the hydrogen (*H) formation energy on the different alloy TPNCs. Thus, utilizing the ligand removal energy as a descriptor for CO₂RR activity and selectivity, our work opens new avenues for accelerated computational screening of different alloy TPNCs for electrocatalytic CO₂R applications.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1982249

Journal Information:: Environmental Science: Nano, Journal Name: Environmental Science: Nano Journal Issue: 6 Vol. 9; ISSN 2051-8153

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Atomically Tailored Gold Nanoclusters for Catalytic Application Higaki, Tatsuya; Li, Yingwei; Zhao, Shuo Angewandte Chemie International Edition, Vol. 58, Issue 25 https://doi.org/10.1002/anie.201814156	journal	March 2019
Hard‐Sphere Random Close‐Packed Au ₄₇ Cd ₂ (TBBT) ₃₁ Nanoclusters with a Faradaic Efficiency of Up to 96 % for Electrocatalytic CO ₂ Reduction to CO Zhuang, Shengli; Chen, Dong; Liao, Lingwen Angewandte Chemie International Edition, Vol. 59, Issue 8 https://doi.org/10.1002/anie.201912845	journal	February 2020
Boosting CO ₂ Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters Li, Site; Nagarajan, Anantha Venkataraman; Alfonso, Dominic R. Angewandte Chemie International Edition, Vol. 60, Issue 12 https://doi.org/10.1002/anie.202016129	journal	February 2021
Electrocatalytic Alloys for CO ₂ Reduction He, Jingfu; Johnson, Noah J. J.; Huang, Aoxue ChemSusChem, Vol. 11, Issue 1 https://doi.org/10.1002/cssc.201701825	journal	December 2017
Global Temperature and Atmospheric Carbon Dioxide Concentration Hashimoto, Koji Global Carbon Dioxide Recycling https://doi.org/10.1007/978-981-13-8584-1_3	book	January 2019
Elucidating the stability of ligand-protected Au nanoclusters under electrochemical reduction of CO2 Nagarajan, Anantha Venkataraman; Juarez-Mosqueda, Rosalba; Cowan, Michael J. SN Applied Sciences, Vol. 2, Issue 4 https://doi.org/10.1007/s42452-020-2488-7	journal	March 2020
CO₂ emission sources, greenhouse gases, and the global warming effect Yoro, Kelvin O.; Daramola, Michael O. Advances in Carbon Capture: Methods, Technologies and Applications https://doi.org/10.1016/B978-0-12-819657-1.00001-3	book	January 2020
Resolving electrocatalytic imprecision in atomically precise metal nanoclusters Nagarajan, Anantha Venkataraman; Loevlie, Dennis Johan; Cowan, Michael J. Current Opinion in Chemical Engineering, Vol. 36 https://doi.org/10.1016/j.coche.2021.100784	journal	June 2022
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures Jin, Rongchao; Li, Gao; Sharma, Sachil Chemical Reviews https://doi.org/10.1021/acs.chemrev.0c00495	journal	September 2020
Synthesis of Ag-Doped Polyoxotitanium Nanoclusters for Efficient Electrocatalytic CO₂ Reduction Liu, Ya-Jie; Shao, Ping; Gao, Mei-Yan Inorganic Chemistry, Vol. 59, Issue 16 https://doi.org/10.1021/acs.inorgchem.0c01245	journal	July 2020
Selective Electrocatalytic Reduction of CO ₂ into CO at Small, Thiol-Capped Au/Cu Nanoparticles Kauffman, Douglas R.; Alfonso, Dominic R.; Tafen, De Nyago The Journal of Physical Chemistry C, Vol. 122, Issue 49 https://doi.org/10.1021/acs.jpcc.8b06234	journal	August 2018
Electrochemical Reduction of Carbon Dioxide on Au Nanoparticles: An in Situ FTIR Study Chen, Shuai; Chen, Aicheng The Journal of Physical Chemistry C, Vol. 123, Issue 39 https://doi.org/10.1021/acs.jpcc.9b04080	journal	July 2019
Rethinking Heterometal Doping in Ligand-Protected Metal Nanoclusters Taylor, Michael G.; Mpourmpakis, Giannis The Journal of Physical Chemistry Letters, Vol. 9, Issue 23 https://doi.org/10.1021/acs.jpclett.8b02679	journal	October 2018
Synergistic Chemisorbing and Electronic Effects for Efficient CO ₂ Reduction Using Cysteamine-Functionalized Gold Nanoparticles Wang, Zhijiang; Sun, Kun; Liang, Caiyun ACS Applied Energy Materials, Vol. 2, Issue 1 https://doi.org/10.1021/acsaem.8b01699	journal	December 2018
Monopalladium Substitution in Gold Nanoclusters Enhances CO ₂ Electroreduction Activity and Selectivity Li, Site; Alfonso, Dominic; Nagarajan, Anantha Venkataraman ACS Catalysis, Vol. 10, Issue 20 https://doi.org/10.1021/acscatal.0c02266	journal	September 2020
Influence of Atomic-Level Morphology on Catalysis: The Case of Sphere and Rod-Like Gold Nanoclusters for CO ₂ Electroreduction Zhao, Shuo; Austin, Natalie; Li, Mo ACS Catalysis, Vol. 8, Issue 6 https://doi.org/10.1021/acscatal.8b00365	journal	April 2018
Opportunities and Challenges in CO ₂ Reduction by Gold- and Silver-Based Electrocatalysts: From Bulk Metals to Nanoparticles and Atomically Precise Nanoclusters Zhao, Shuo; Jin, Renxi; Jin, Rongchao ACS Energy Letters, Vol. 3, Issue 2 https://doi.org/10.1021/acsenergylett.7b01104	journal	January 2018
Aqueous CO ₂ Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles Chen, Yihong; Li, Christina W.; Kanan, Matthew W. Journal of the American Chemical Society, Vol. 134, Issue 49 https://doi.org/10.1021/ja309317u	journal	November 2012
Hydrogen Evolution Electrocatalyst Design: Turning Inert Gold into Active Catalyst by Atomically Precise Nanochemistry Li, Yingwei; Li, Site; Nagarajan, Anantha V. Journal of the American Chemical Society, Vol. 143, Issue 29 https://doi.org/10.1021/jacs.1c04606	journal	July 2021
Size-Dependent Electrocatalytic Reduction of CO ₂ over Pd Nanoparticles Gao, Dunfeng; Zhou, Hu; Wang, Jing Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/jacs.5b00046	journal	March 2015
Mono-Mercury Doping of Au ₂₅ and the HOMO/LUMO Energies Evaluation Employing Differential Pulse Voltammetry Liao, Lingwen; Zhou, Shiming; Dai, Yafei Journal of the American Chemical Society, Vol. 137, Issue 30 https://doi.org/10.1021/jacs.5b03483	journal	July 2015
Achieving Selective and Efficient Electrocatalytic Activity for CO ₂ Reduction Using Immobilized Silver Nanoparticles Kim, Cheonghee; Jeon, Hyo Sang; Eom, Taedaehyeong Journal of the American Chemical Society, Vol. 137, Issue 43 https://doi.org/10.1021/jacs.5b06568	journal	October 2015
Mono-cadmium vs Mono-mercury Doping of Au ₂₅ Nanoclusters Yao, Chuanhao; Lin, Yue-jian; Yuan, Jinyun Journal of the American Chemical Society, Vol. 137, Issue 49 https://doi.org/10.1021/jacs.5b09627	journal	December 2015
Metal Doping of Au ₂₅ (SR) ₁₈ ^– Clusters: Insights and Hindsights Fei, Wenwen; Antonello, Sabrina; Dainese, Tiziano Journal of the American Chemical Society, Vol. 141, Issue 40 https://doi.org/10.1021/jacs.9b08228	journal	September 2019
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
Divide and Protect: Capping Gold Nanoclusters with Molecular Gold−Thiolate Rings Häkkinen, Hannu; Walter, Michael; Grönbeck, Henrik The Journal of Physical Chemistry B, Vol. 110, Issue 20 https://doi.org/10.1021/jp0619787	journal	May 2006
Electron Injection from Colloidal PbS Quantum Dots into Titanium Dioxide Nanoparticles Hyun, Byung-Ryool; Zhong, Yu-Wu.; Bartnik, Adam C. ACS Nano, Vol. 2, Issue 11 https://doi.org/10.1021/nn800336b	journal	October 2008
Thermodynamic stability of ligand-protected metal nanoclusters Taylor, Michael G.; Mpourmpakis, Giannis Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15988	journal	July 2017
Structures and magnetism of mono-palladium and mono-platinum doped Au ₂₅ (PET) ₁₈ nanoclusters Tian, Shubo; Liao, Lingwen; Yuan, Jinyun Chemical Communications, Vol. 52, Issue 64 https://doi.org/10.1039/C6CC02698B	journal	January 2016
The impact of size and shape distributions on the electron charge transfer properties of silver nanoparticles Sun, Baichuan; Barnard, Amanda S. Nanoscale, Vol. 9, Issue 34 https://doi.org/10.1039/C7NR03472E	journal	January 2017
New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO ₂ into hydrocarbon chemicals and fuels Zhou, Wei; Cheng, Kang; Kang, Jincan Chemical Society Reviews, Vol. 48, Issue 12 https://doi.org/10.1039/C8CS00502H	journal	January 2019
Elucidating the active sites for CO ₂ electroreduction on ligand-protected Au ₂₅ nanoclusters Austin, Natalie; Zhao, Shuo; McKone, James R. Catalysis Science & Technology, Vol. 8, Issue 15 https://doi.org/10.1039/C8CY01099D	journal	January 2018
Au ₂₅ (SR) ₁₈ : the captain of the great nanocluster ship Kang, Xi; Chong, Hanbao; Zhu, Manzhou Nanoscale, Vol. 10, Issue 23 https://doi.org/10.1039/C8NR02973C	journal	January 2018
Atomically precise alloy nanoclusters: syntheses, structures, and properties Kang, Xi; Li, Yingwei; Zhu, Manzhou Chemical Society Reviews, Vol. 49, Issue 17 https://doi.org/10.1039/C9CS00633H	journal	January 2020
Integrated design for electrocatalytic carbon dioxide reduction Zhao, Xin; Du, Lijie; You, Bo Catalysis Science & Technology, Vol. 10, Issue 9 https://doi.org/10.1039/D0CY00453G	journal	January 2020
Towards elucidating structure of ligand-protected nanoclusters Cowan, Michael J.; Mpourmpakis, Giannis Dalton Transactions, Vol. 49, Issue 27 https://doi.org/10.1039/D0DT01418D	journal	January 2020
The role of ligands in atomically precise nanocluster-catalyzed CO₂ electrochemical reduction Li, Site; Nagarajan, Anantha Venkataraman; Li, Yingwei Nanoscale, Vol. 13, Issue 4 https://doi.org/10.1039/D0NR07832H	journal	January 2021
Predicting ligand removal energetics in thiolate-protected nanoclusters from molecular complexes McKay, Julia; Cowan, Michael J.; Morales-Rivera, Cristian A. Nanoscale, Vol. 13, Issue 3 https://doi.org/10.1039/D0NR07839E	journal	January 2021
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
Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases VandeVondele, Joost; Hutter, Jürg The Journal of Chemical Physics, Vol. 127, Issue 11 https://doi.org/10.1063/1.2770708	journal	September 2007
Active sites of ligand-protected Au ₂₅ nanoparticle catalysts for CO ₂ electroreduction to CO Alfonso, Dominic R.; Kauffman, Douglas; Matranga, Christopher The Journal of Chemical Physics, Vol. 144, Issue 18 https://doi.org/10.1063/1.4948792	journal	May 2016
CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations Kühne, Thomas D.; Iannuzzi, Marcella; Del Ben, Mauro The Journal of Chemical Physics, Vol. 152, Issue 19 https://doi.org/10.1063/5.0007045	journal	May 2020
Correlating structural rules with electronic properties of ligand-protected alloy nanoclusters Cowan, Michael J.; Nagarajan, Anantha Venkataraman; Mpourmpakis, Giannis The Journal of Chemical Physics, Vol. 155, Issue 2 https://doi.org/10.1063/5.0056690	journal	July 2021
Controlled syngas production by electrocatalytic CO₂ reduction on formulated Au₂₅(SR)₁₈ and PtAu₂₄(SR)₁₈ nanoclusters Choi, Woojun; Seong, Hoeun; Efremov, Vladimir The Journal of Chemical Physics, Vol. 155, Issue 1 https://doi.org/10.1063/5.0057470	journal	July 2021
Separable dual-space Gaussian pseudopotentials Goedecker, S.; Teter, M.; Hutter, J. Physical Review B, Vol. 54, Issue 3 https://doi.org/10.1103/PhysRevB.54.1703	journal	July 1996
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Unfolding adsorption on metal nanoparticles: Connecting stability with catalysis Dean, James; Taylor, Michael G.; Mpourmpakis, Giannis Science Advances, Vol. 5, Issue 9 https://doi.org/10.1126/sciadv.aax5101	journal	September 2019
Electrocatalytic Reduction of CO ₂ at Au Nanoparticle Electrodes: Effects of Interfacial Chemistry on Reduction Behavior Andrews, Evan; Katla, Sai; Kumar, Challa Journal of The Electrochemical Society, Vol. 162, Issue 12 https://doi.org/10.1149/2.0541512jes	journal	January 2015

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