Electron injection study of photoexcitation effects on supported subnanometer Pt clusters for CO2 photoreduction

Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.; Joseph, Babu

doi:10.1039/C8CP00619A

Title: Electron injection study of photoexcitation effects on supported subnanometer Pt clusters for CO₂ photoreduction

Journal Article · Thu May 10 00:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C8CP00619A· OSTI ID:1465295

^[1];

^[2];

^[1];

^[1]

Univ. of South Florida, Tampa, FL (United States). Dept. of Chemical and Biomedical Engineering
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division

In this paper, using density functional theory, we study the effect of injected electrons (simulating photoexcited electrons) on the energetics, structures, and binding sites available to CO₂ molecules on subnanometer Pt clusters decorated onto anatase TiO₂(101) surfaces, shedding light on the first and key step of CO₂ photoreduction. Upon the addition of one, two, or three electrons, the O–C–O angles of adsorbed CO₂ become progressively smaller in binding sites that directly contact Pt clusters, while no significant change is found in the intra bond length of the adsorbed CO₂ and in the bonding distances between the adsorbed CO₂ and supported clusters. The extra electrons lead to the stabilization of adsorption sites identified on neutral slabs, including previously metastable configurations, suggesting the enhancement of accessible CO₂ binding sites. Furthermore, supported clusters are able to populate the electronic states of adsorbed CO₂ species, facilitating the formation of the CO₂^- anion. To help interpret experimentally observed frequencies, conversion factors are proposed to gain insight into the charge state and O–C–O angle of the adsorbed CO₂. Interestingly, upon electron addition, cluster reconstruction may exist due to the bonding inclination between CO₂ and atoms in the Pt cluster, further stabilizing the intermediate complexes. In conclusion, the rate-limiting step (C–O bond cleavage) in the CO₂ dissociation to CO is slightly reduced by the introduction of an extra electron. Our results show that subnanometer metal cluster based photocatalysts are good candidates for CO₂ photoreduction.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of South Florida, Tampa, FL (United States)

Sponsoring Organization:: USDOE; LLNL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)

Grant/Contract Number:: AC52-07NA27344; CHE-1531590

OSTI ID:: 1465295

Alternate ID(s):: OSTI ID: 1439755

Report Number(s):: LLNL-JRNL-745700; 900486

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 23; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

References (58)

Influence of Subsurface Defects on the Surface Reactivity of TiO ₂ : Water on Anatase (101) Aschauer, Ulrich; He, Yunbin; Cheng, Hongzhi The Journal of Physical Chemistry C, Vol. 114, Issue 2 https://doi.org/10.1021/jp910492b	journal	December 2009
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
Density-functional calculation of effective Coulomb interactions in metals Anisimov, V. I.; Gunnarsson, O. Physical Review B, Vol. 43, Issue 10, p. 7570-7574 https://doi.org/10.1103/PhysRevB.43.7570	journal	April 1991
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Effects of subnanometer silver clusters on the AgBr(110) photocatalyst surface: a theoretical investigation Chi, Yuhua; Zhao, Lianming; Lu, Xiaoqing Catalysis Science & Technology, Vol. 5, Issue 10 https://doi.org/10.1039/C5CY00705D	journal	January 2015
A surface science perspective on TiO2 photocatalysis Henderson, Michael A. Surface Science Reports, Vol. 66, Issue 6-7 https://doi.org/10.1016/j.surfrep.2011.01.001	journal	June 2011
The effect of the morphology of supported subnanometer Pt clusters on the first and key step of CO ₂ photoreduction Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R. Physical Chemistry Chemical Physics, Vol. 17, Issue 38 https://doi.org/10.1039/C5CP03674G	journal	January 2015
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
Role of Four-Fold Coordinated Titanium and Quantum Confinement in CO ₂ Reduction at Titania Surface Lee, Donghwa; Kanai, Yosuke Journal of the American Chemical Society, Vol. 134, Issue 50 https://doi.org/10.1021/ja309871m	journal	December 2012
Size-Selective Reactivity of Subnanometer Ag ₄ and Ag ₁₆ Clusters on a TiO ₂ Surface Chen, Po-Tuan; Tyo, Eric C.; Hayashi, Michitoshi The Journal of Physical Chemistry C, Vol. 121, Issue 12 https://doi.org/10.1021/acs.jpcc.6b11375	journal	March 2017
The electronic structure effect in heterogeneous catalysis Nilsson, A.; Pettersson, L. G. M.; Hammer, B. Catalysis Letters, Vol. 100, Issue 3-4 https://doi.org/10.1007/s10562-004-3434-9	journal	April 2005
Effect of TiO2 support on the structural and electronic properties of PdmAgn clusters: a first-principles study Han, You; Zhang, Ming; Li, Wei Physical Chemistry Chemical Physics, Vol. 14, Issue 24 https://doi.org/10.1039/c2cp40562h	journal	January 2012
Single-atom catalysis of CO oxidation using Pt1/FeOx Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1095	journal	July 2011
A Theoretical Study of CO ₂ Anions on Anatase (101) Surface He, Haiying; Zapol, Peter; Curtiss, Larry A. The Journal of Physical Chemistry C, Vol. 114, Issue 49 https://doi.org/10.1021/jp106579b	journal	November 2010
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Computational screening of dopants for photocatalytic two-electron reduction of CO2 on anatase (101) surfaces He, Haiying; Zapol, Peter; Curtiss, Larry A. Energy & Environmental Science, Vol. 5, Issue 3 https://doi.org/10.1039/c2ee02665a	journal	January 2012
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Directly converting CO2 into a gasoline fuel Wei, Jian; Ge, Qingjie; Yao, Ruwei Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15174	journal	May 2017
Carbon dioxide activation and dissociation on ceria (110): A density functional theory study Cheng, Zhuo; Sherman, Brent J.; Lo, Cynthia S. The Journal of Chemical Physics, Vol. 138, Issue 1, Article No. 014702 https://doi.org/10.1063/1.4773248	journal	January 2013
Morphological effects of Au 13 clusters on the adsorption of CO 2 over anatase TiO 2 (101) Liu, Li; Liu, Zhongbo; Sun, Honggang Applied Surface Science, Vol. 399 https://doi.org/10.1016/j.apsusc.2016.12.089	journal	March 2017
Anatase shows its reactive side Selloni, Annabella Nature Materials, Vol. 7, Issue 8 https://doi.org/10.1038/nmat2241	journal	August 2008
Magic Number Pt ₁₃ and Misshapen Pt ₁₂ Clusters: Which One is the Better Catalyst? Imaoka, Takane; Kitazawa, Hirokazu; Chun, Wang-Jae Journal of the American Chemical Society, Vol. 135, Issue 35 https://doi.org/10.1021/ja405922m	journal	August 2013
Photocatalytic Process for CO ₂ Emission Reduction from Industrial Flue Gas Streams Usubharatana, Phairat; McMartin, Dena; Veawab, Amornvadee Industrial & Engineering Chemistry Research, Vol. 45, Issue 8 https://doi.org/10.1021/ie0505763	journal	April 2006
Interplay between Subnanometer Ag and Pt Clusters and Anatase TiO ₂ (101) Surface: Implications for Catalysis and Photocatalysis Yang, Chi-Ta; Balakrishnan, Nianthrini; Bhethanabotla, Venkat R. The Journal of Physical Chemistry C, Vol. 118, Issue 9 https://doi.org/10.1021/jp4112525	journal	February 2014
Surface Phases of TiO ₂ Nanoparticles Studied by UV Raman Spectroscopy and FT-IR Spectroscopy Su, Weiguang; Zhang, Jing; Feng, Zhaochi The Journal of Physical Chemistry C, Vol. 112, Issue 20 https://doi.org/10.1021/jp7118422	journal	April 2008
Increased Silver Activity for Direct Propylene Epoxidation via Subnanometer Size Effects Lei, Y.; Mehmood, F.; Lee, S. Science, Vol. 328, Issue 5975, p. 224-228 https://doi.org/10.1126/science.1185200	journal	April 2010
Adsorption CO2 on the perfect and oxygen vacancy defect surfaces of anatase TiO2 and its photocatalytic mechanism of conversion to CO Pipornpong, Waranyu; Wanbayor, Raina; Ruangpornvisuti, Vithaya Applied Surface Science, Vol. 257, Issue 24 https://doi.org/10.1016/j.apsusc.2011.06.013	journal	October 2011
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Infrared Spectroscopic Study of the Photoinduced Activation of CO2 on TiO2 and Rh/TiO2 Catalysts Rasko, Janos; Solymosi, Frigyes The Journal of Physical Chemistry, Vol. 98, Issue 29 https://doi.org/10.1021/j100080a009	journal	July 1994
Charging Effects on Bonding and Catalyzed Oxidation of CO on Au₈ Clusters on MgO Yoon, Bokwon; Häkkinen, Hannu; Landman, Uzi Science, Vol. 307, Issue 5708, p. 403-407 https://doi.org/10.1126/science.1104168	journal	January 2005
Activation of CO ₂ by supported Cu clusters Iyemperumal, Satish Kumar; Deskins, N. Aaron Physical Chemistry Chemical Physics, Vol. 19, Issue 42 https://doi.org/10.1039/C7CP05718K	journal	January 2017
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Morphological Effects of Gold Clusters on the Reactivity of Ceria Surface Oxygen Wang, Jin; Tan, Hongyi; Yu, Shuzhen ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/cs502055r	journal	March 2015
CO ₂ Adsorption on Anatase TiO ₂ (101) Surfaces in the Presence of Subnanometer Ag/Pt Clusters: Implications for CO ₂ Photoreduction Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R. The Journal of Physical Chemistry C, Vol. 118, Issue 45 https://doi.org/10.1021/jp509219n	journal	November 2014
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
CO ₂ adsorption on TiO ₂ (101) anatase: A dispersion-corrected density functional theory study Sorescu, Dan C.; Al-Saidi, Wissam A.; Jordan, Kenneth D. The Journal of Chemical Physics, Vol. 135, Issue 12 https://doi.org/10.1063/1.3638181	journal	September 2011
Adsorption of Pt and Bimetallic PtAu Clusters on the Partially Reduced Rutile (110) TiO ₂ Surface: A First-Principles Study Çakır, D.; Gülseren, O. The Journal of Physical Chemistry C, Vol. 116, Issue 9 https://doi.org/10.1021/jp2109253	journal	February 2012
Optimization methods for finding minimum energy paths Sheppard, Daniel; Terrell, Rye; Henkelman, Graeme The Journal of Chemical Physics, Vol. 128, Issue 13 https://doi.org/10.1063/1.2841941	journal	April 2008
Photocatalytic Reduction of CO ₂ on TiO ₂ and Other Semiconductors Habisreutinger, Severin N.; Schmidt-Mende, Lukas; Stolarczyk, Jacek K. Angewandte Chemie International Edition, Vol. 52, Issue 29 https://doi.org/10.1002/anie.201207199	journal	June 2013
Photoinduced activation of CO2 on Ti-based heterogeneous catalysts: Current state, chemical physics-based insights and outlook Indrakanti, Venkata Pradeep; Kubicki, James D.; Schobert, Harold H. Energy & Environmental Science, Vol. 2, Issue 7 https://doi.org/10.1039/b822176f	journal	January 2009
Toward Solar Fuels: Photocatalytic Conversion of Carbon Dioxide to Hydrocarbons Roy, Somnath C.; Varghese, Oomman K.; Paulose, Maggie ACS Nano, Vol. 4, Issue 3 https://doi.org/10.1021/nn9015423	journal	February 2010
CO ₂ adsorption on anatase TiO ₂ (101) surfaces: a combination of UHV-FTIRS and first-principles studies Cao, Yunjun; Yu, Min; Qi, Shandong Physical Chemistry Chemical Physics, Vol. 19, Issue 46 https://doi.org/10.1039/C7CP05375D	journal	January 2017
Improved grid-based algorithm for Bader charge allocation Sanville, Edward; Kenny, Steven D.; Smith, Roger Journal of Computational Chemistry, Vol. 28, Issue 5 https://doi.org/10.1002/jcc.20575	journal	January 2007
Towards the computational design of solid catalysts Nørskov, J.; Bligaard, T.; Rossmeisl, J. Nature Chemistry, Vol. 1, Issue 1, p. 37-46 https://doi.org/10.1038/nchem.121	journal	April 2009
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
CO ₂ Capture by TiO ₂ Anatase Surfaces: A Combined DFT and FTIR Study Mino, Lorenzo; Spoto, Giuseppe; Ferrari, Anna Maria The Journal of Physical Chemistry C, Vol. 118, Issue 43 https://doi.org/10.1021/jp507443k	journal	October 2014
Quantum Chemical Modeling of Ground States of CO ₂ Chemisorbed on Anatase (001), (101), and (010) TiO ₂ Surfaces Indrakanti, Venkata Pradeep; Kubicki, James D.; Schobert, Harold H. Energy & Fuels, Vol. 22, Issue 4 https://doi.org/10.1021/ef700725u	journal	July 2008
Structural, Electronic, and Impurity-Doping Effects in Nanoscale Chemistry: Supported Gold Nanoclusters Häkkinen, Hannu; Abbet, Stéphane; Sanchez, Antonio Angewandte Chemie International Edition, Vol. 42, Issue 11 https://doi.org/10.1002/anie.200390334	journal	March 2003
First principles theoretical study of the hole-assisted conversion of CO to CO ₂ on the anatase TiO ₂ (101) surface Wanbayor, Raina; Deák, Peter; Frauenheim, Thomas The Journal of Chemical Physics, Vol. 134, Issue 10 https://doi.org/10.1063/1.3562366	journal	March 2011
Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane Vajda, Stefan; Pellin, Michael J.; Greeley, Jeffrey P. Nature Materials, Vol. 8, Issue 3 https://doi.org/10.1038/nmat2384	journal	February 2009
A theoretical study of CO2 adsorption on TiO2 Markovits, Alexis; Fahmi, Adil; Minot, Christian Journal of Molecular Structure: THEOCHEM, Vol. 371 https://doi.org/10.1016/S0166-1280(96)04696-9	journal	November 1996
A Density Functional Theory and Experimental Study of CO ₂ Interaction with Brookite TiO ₂ Rodriguez, Monique M.; Peng, Xihong; Liu, Lianjun The Journal of Physical Chemistry C, Vol. 116, Issue 37 https://doi.org/10.1021/jp302342t	journal	September 2012
Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy Linic, Suljo; Christopher, Phillip; Ingram, David B. Nature Materials, Vol. 10, Issue 12 https://doi.org/10.1038/nmat3151	journal	November 2011
Strong metal-support interactions Tauster, S. J. Accounts of Chemical Research, Vol. 20, Issue 11 https://doi.org/10.1021/ar00143a001	journal	November 1987
Structural, Electronic, and Impurity-Doping Effects in Nanoscale Chemistry: Supported Gold Nanoclusters. Haekkinen, Hannu; Abbet, Stephane; Sanchez, Antonio ChemInform, Vol. 34, Issue 21 https://doi.org/10.1002/chin.200321014	journal	May 2003
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
Lead palladium titanate: A room temperature nanoscale multiferroic thin film Mishra, K. K.; Instan, Alvaro A.; Kumari, Shalini Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-59961-w	journal	February 2020

Similar Records

The effect of the morphology of supported subnanometer Pt clusters on the first and key step of CO₂ photoreduction [Morphology effect of supported subnanometer Pt clusters on first and key step of CO₂ photoreduction]

Journal Article · Fri Sep 04 00:00:00 EDT 2015 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1465295

Yang, Chi -Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.; +1 more

CO ₂ Adsorption on Anatase TiO ₂ (101) Surfaces in the Presence of Subnanometer Ag/Pt Clusters: Implications for CO ₂ Photoreduction

Journal Article · Mon Oct 20 00:00:00 EDT 2014 · Journal of Physical Chemistry. C · OSTI ID:1465295

Yang, Chi-Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.; +1 more

Density functional studies of methanol decomposition on subnanometer Pd clusters.

Journal Article · Thu Dec 31 00:00:00 EST 2009 · J. Phys. Chem. C · OSTI ID:1465295

Mehmood, F; Greeley, J; Curtiss, L A

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS

Title: Electron injection study of photoexcitation effects on supported subnanometer Pt clusters for CO2 photoreduction

Citation Formats

References (58)

Similar Records

Related Subjects

Title: Electron injection study of photoexcitation effects on supported subnanometer Pt clusters for CO₂ photoreduction