Imaging Catalytic Activation of CO2 on Cu2O (110): A First-Principles Study

Li, Liang; Zhang, Rui; Vinson, John; Shirley, Eric L.; Greeley, Jeffrey P.; Guest, Jeffrey R.; Chan, Maria K. Y.

doi:10.1021/acs.chemmater.7b04803

Title: Imaging Catalytic Activation of CO₂ on Cu₂O (110): A First-Principles Study

Journal Article · 05 March 2018 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.7b04803 · OSTI ID:1434330

^[1]; Zhang, Rui ^[1];

^[2]; Shirley, Eric L. ^[2];

^[3];

^[1];

^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Purdue Univ., West Lafayette, IN (United States)

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO₂ reduction. While photoreduction of CO₂ is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu₂O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO₂ and the Cu₂O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu₂O (110) surface stoichiometry that favors CO₂ reduction. To facilitate interpretation of scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO₂ reduction reaction on, and rational surface engineering of, Cu₂O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1434330

Journal Information:: Chemistry of Materials, Vol. 30, Issue 6; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (94)

Alternative energy technologies Dresselhaus, M. S.; Thomas, I. L. Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104599	journal	November 2001
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
Recent advances in hybrid photocatalysts for solar fuel production Tran, Phong D.; Wong, Lydia H.; Barber, James Energy & Environmental Science, Vol. 5, Issue 3 https://doi.org/10.1039/c2ee02849b	journal	January 2012
Photoelectrocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders Inoue, Tooru; Fujishima, Akira; Konishi, Satoshi Nature, Vol. 277, Issue 5698 https://doi.org/10.1038/277637a0	journal	February 1979
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar9001679	journal	December 2009
High-Rate Solar Photocatalytic Conversion of CO ₂ and Water Vapor to Hydrocarbon Fuels Varghese, Oomman K.; Paulose, Maggie; LaTempa, Thomas J. Nano Letters, Vol. 9, Issue 2 https://doi.org/10.1021/nl803258p	journal	February 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
Heterogeneous catalytic conversion of CO ₂ : a comprehensive theoretical review Li, Yawei; Chan, Siew Hwa; Sun, Qiang Nanoscale, Vol. 7, Issue 19 https://doi.org/10.1039/C5NR00092K	journal	January 2015
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
Chemical Role of Holes and Electrons in ZnO Photocatalysis Morrison, S. R.; Freund, T. The Journal of Chemical Physics, Vol. 47, Issue 4 https://doi.org/10.1063/1.1712115	journal	August 1967
Photocatalysis Using ZnO Thin Films and Nanoneedles Grown by Metal-Organic Chemical Vapor Deposition Yang, J. L.; An, S. J.; Park, W. I. Advanced Materials, Vol. 16, Issue 18 https://doi.org/10.1002/adma.200306673	journal	September 2004
Photooxidation of Water at α-Fe[sub 2]O[sub 3] Electrodes Kennedy, John H. Journal of The Electrochemical Society, Vol. 125, Issue 5 https://doi.org/10.1149/1.2131532	journal	January 1978
Sn-Doped Hematite Nanostructures for Photoelectrochemical Water Splitting Ling, Yichuan; Wang, Gongming; Wheeler, Damon A. Nano Letters, Vol. 11, Issue 5 https://doi.org/10.1021/nl200708y	journal	May 2011
Reduction of Carbon Dioxide to Methanol on n- and p-GaAs and p-InP. Effect of Crystal Face, Electrolyte and Current Density Canfield, D. Journal of The Electrochemical Society, Vol. 130, Issue 8 https://doi.org/10.1149/1.2120090	journal	January 1983
Electrochemical measurement on the photoelectrochemical reduction of aqueous carbon dioxide on p-Gallium phosphide and p-Gallium arsenide semiconductor electrodes Aurian-Blajeni, B.; Halmann, M.; Manassen, J. Solar Energy Materials, Vol. 8, Issue 4, p. 425-440 https://doi.org/10.1016/0165-1633(83)90007-2	journal	March 1983
Electrochemical Photolysis of Water at a Semiconductor Electrode Fujishima, Akira; Honda, Kenichi Nature, Vol. 238, Issue 5358, p. 37-38 https://doi.org/10.1038/238037a0	journal	July 1972
Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals Chen, X.; Liu, L.; Yu, P. Y. Science, Vol. 331, Issue 6018 https://doi.org/10.1126/science.1200448	journal	January 2011
Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a013	journal	May 1995
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
Role of Water and Carbonates in Photocatalytic Transformation of CO ₂ to CH ₄ on Titania Dimitrijevic, Nada M.; Vijayan, Baiju K.; Poluektov, Oleg G. Journal of the American Chemical Society, Vol. 133, Issue 11 https://doi.org/10.1021/ja108791u	journal	March 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
Engineering TiO2 nanomaterials for CO2 conversion/solar fuels Liu, Guohua; Hoivik, Nils; Wang, Kaiying Solar Energy Materials and Solar Cells, Vol. 105 https://doi.org/10.1016/j.solmat.2012.05.037	journal	October 2012
Fine structure of excitons in Cu 2 O Kavoulakis, G. M.; Chang, Yia-Chung; Baym, Gordon Physical Review B, Vol. 55, Issue 12 https://doi.org/10.1103/PhysRevB.55.7593	journal	March 1997
Band-structure calculations for the 3 d transition metal oxides in G W Lany, Stephan Physical Review B, Vol. 87, Issue 8 https://doi.org/10.1103/PhysRevB.87.085112	journal	February 2013
The impact of surface structure and band gap on the optoelectronic properties of Cu2O nanoclusters of varying size and symmetry Sinha, Banita; Goswami, Tamal; Paul, Satadal RSC Advances, Vol. 4, Issue 10 https://doi.org/10.1039/c3ra45387a	journal	January 2014
Sonochemical synthesis and photocatalysis of porous Cu ₂ O nanospheres with controllable structures Xu, Lang; Jiang, Li-Ping; Zhu, Jun-Jie Nanotechnology, Vol. 20, Issue 4 https://doi.org/10.1088/0957-4484/20/4/045605	journal	December 2008
Cu2O as a photocatalyst for overall water splitting under visible light irradiation Hara, Michikazu; Kondo, Takeshi; Komoda, Mutsuko Chemical Communications, Issue 3 https://doi.org/10.1039/a707440i	journal	January 1998
Binary copper oxide semiconductors: From materials towards devices Meyer, B. K.; Polity, A.; Reppin, D. physica status solidi (b), Vol. 249, Issue 8 https://doi.org/10.1002/pssb.201248128	journal	June 2012
First-Principles Predictions of the Structure, Stability, and Photocatalytic Potential of Cu ₂ O Surfaces Bendavid, Leah Isseroff; Carter, Emily A. The Journal of Physical Chemistry B, Vol. 117, Issue 49 https://doi.org/10.1021/jp406454c	journal	September 2013
Tailoring Copper Oxide Semiconductor Nanorod Arrays for Photoelectrochemical Reduction of Carbon Dioxide to Methanol Rajeshwar, Krishnan; de Tacconi, Norma R.; Ghadimkhani, Ghazaleh ChemPhysChem, Vol. 14, Issue 10 https://doi.org/10.1002/cphc.201300080	journal	May 2013
Efficient solar photoelectrosynthesis of methanol from carbon dioxide using hybrid CuO–Cu2O semiconductor nanorod arrays Ghadimkhani, Ghazaleh; de Tacconi, Norma R.; Chanmanee, Wilaiwan Chemical Communications, Vol. 49, Issue 13 https://doi.org/10.1039/c2cc38068d	journal	January 2013
Porous-structured Cu ₂ O/TiO ₂ nanojunction material toward efficient CO ₂ photoreduction Xu, Hua; Ouyang, Shuxin; Liu, Lequan Nanotechnology, Vol. 25, Issue 16 https://doi.org/10.1088/0957-4484/25/16/165402	journal	March 2014
Enhanced Photoreduction CO ₂ Activity over Direct Z-Scheme α-Fe ₂ O ₃ /Cu ₂ O Heterostructures under Visible Light Irradiation Wang, Ji-Chao; Zhang, Lin; Fang, Wen-Xue ACS Applied Materials & Interfaces, Vol. 7, Issue 16 https://doi.org/10.1021/acsami.5b00822	journal	April 2015
Shape Evolution and Size-Controllable Synthesis of Cu ₂ O Octahedra and Their Morphology-Dependent Photocatalytic Properties Xu, Haolan; Wang, Wenzhong; Zhu, Wei The Journal of Physical Chemistry B, Vol. 110, Issue 28 https://doi.org/10.1021/jp061934y	journal	July 2006
Crystal Faces of Cu ₂ O and Their Stabilities in Photocatalytic Reactions Zheng, Zhaoke; Huang, Baibiao; Wang, Zeyan The Journal of Physical Chemistry C, Vol. 113, Issue 32 https://doi.org/10.1021/jp904198d	journal	July 2009
Synthesis of Cu ₂ O Nanocrystals from Cubic to Rhombic Dodecahedral Structures and Their Comparative Photocatalytic Activity Huang, Wan-Chen; Lyu, Lian-Ming; Yang, Yu-Chen Journal of the American Chemical Society, Vol. 134, Issue 2 https://doi.org/10.1021/ja209662v	journal	December 2011
Bulk and surface properties of Cu2O: A first-principles investigation Islam, Mazharul M.; Diawara, Boubakar; Maurice, Vincent Journal of Molecular Structure: THEOCHEM, Vol. 903, Issue 1-3 https://doi.org/10.1016/j.theochem.2009.02.037	journal	June 2009
A computational study on water adsorption on Cu2O(111) surfaces: The effects of coverage and oxygen defect Yu, Xiaohu; Zhang, Xuemei; Wang, Shengguang Applied Surface Science, Vol. 343 https://doi.org/10.1016/j.apsusc.2015.03.065	journal	July 2015
Atomic structure of Cu2O(111) Önsten, Anneli; Göthelid, Mats; Karlsson, Ulf O. Surface Science, Vol. 603, Issue 2 https://doi.org/10.1016/j.susc.2008.10.048	journal	January 2009
CO ₂ Adsorption on Cu ₂ O(111): A DFT+U and DFT-D Study Bendavid, Leah Isseroff; Carter, Emily A. The Journal of Physical Chemistry C, Vol. 117, Issue 49 https://doi.org/10.1021/jp407468t	journal	November 2013
Role of Defects in Surface Chemistry on Cu ₂ O(111) Önsten, Anneli; Weissenrieder, Jonas; Stoltz, Dunja The Journal of Physical Chemistry C, Vol. 117, Issue 38 https://doi.org/10.1021/jp3112217	journal	September 2013
Cooperative Effects in Water Binding to Cuprous Oxide Surfaces Riplinger, Christoph; Carter, Emily A. The Journal of Physical Chemistry C, Vol. 119, Issue 17 https://doi.org/10.1021/acs.jpcc.5b00383	journal	April 2015
Density functional theory periodic slab calculations of adsorption and dissociation of H ₂ O on the Cu ₂ O(110):CuO surface Saraireh, Sherin A.; Altarawneh, Mohammednoor Canadian Journal of Physics, Vol. 91, Issue 12 https://doi.org/10.1139/cjp-2013-0272	journal	December 2013
Opportunities and prospects in the chemical recycling of carbon dioxide to fuels Centi, Gabriele; Perathoner, Siglinda Catalysis Today, Vol. 148, Issue 3-4 https://doi.org/10.1016/j.cattod.2009.07.075	journal	November 2009
The bending machine: CO ₂ activation and hydrogenation on δ-MoC(001) and β-Mo ₂ C(001) surfaces Posada-Pérez, Sergio; Viñes, Francesc; Ramirez, Pedro J. Phys. Chem. Chem. Phys., Vol. 16, Issue 28 https://doi.org/10.1039/C4CP01943A	journal	January 2014
Hydrogenation of CO ₂ to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO ₂ Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J. ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01755	journal	October 2015
Photocatalytic CO ₂ Reduction with H ₂ O on TiO ₂ Nanocrystals: Comparison of Anatase, Rutile, and Brookite Polymorphs and Exploration of Surface Chemistry Liu, Lianjun; Zhao, Huilei; Andino, Jean M. ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs300273q	journal	July 2012
Synthesis, Characterization, Electronic Structure, and Photocatalytic Behavior of CuGaO ₂ and CuGa _{1– x} Fe _x O ₂ ( x = 0.05, 0.10, 0.15, 0.20) Delafossites Lekse, Jonathan W.; Underwood, M. Kylee; Lewis, James P. The Journal of Physical Chemistry C, Vol. 116, Issue 2 https://doi.org/10.1021/jp2087225	journal	January 2012
CO 2 dissociation activated through electron attachment on the reduced rutile TiO 2 (110)-1 × 1 surface Tan, Shijing; Zhao, Yan; Zhao, Jin Physical Review B, Vol. 84, Issue 15 https://doi.org/10.1103/PhysRevB.84.155418	journal	October 2011
Modelling STM images of TiO2(110) from first-principles: Defects, water adsorption and dissociation products Teobaldi, G.; Hofer, W. A.; Bikondoa, O. Chemical Physics Letters, Vol. 437, Issue 1-3 https://doi.org/10.1016/j.cplett.2007.01.068	journal	March 2007
XANES Study of Cu ²⁺ -Binding Sites in Aquatic Humic Substances Frenkel, Anatoly I.; Korshin, Gregory V.; Ankudinov, Alexei L. Environmental Science & Technology, Vol. 34, Issue 11 https://doi.org/10.1021/es990561u	journal	June 2000
A Comparative Study of the Methods of Speciation Using X-ray Absorption Fine Structure Gaur, A.; Shrivastava, B. D. Acta Physica Polonica A, Vol. 121, Issue 3 https://doi.org/10.12693/APhysPolA.121.647	journal	March 2012
Carbon Dioxide Conversion to Methanol over Size-Selected Cu ₄ Clusters at Low Pressures Liu, Cong; Yang, Bing; Tyo, Eric Journal of the American Chemical Society, Vol. 137, Issue 27 https://doi.org/10.1021/jacs.5b03668	journal	July 2015
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
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
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
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
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Oxidation energies of transition metal oxides within the GGA + U framework Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand Physical Review B, Vol. 73, Issue 19 https://doi.org/10.1103/PhysRevB.73.195107	journal	May 2006
Semiempirical GGA-type density functional constructed with a long-range dispersion correction Grimme, Stefan Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799 https://doi.org/10.1002/jcc.20495	journal	January 2006
A dispersion-corrected density functional theory case study on ethyl acetate conformers, dimer, and molecular crystal Brandenburg, Jan Gerit; Grimme, Stefan Theoretical Chemistry Accounts, Vol. 132, Issue 11 https://doi.org/10.1007/s00214-013-1399-8	journal	September 2013
Chemical accuracy for the van der Waals density functional Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Journal of Physics: Condensed Matter, Vol. 22, Issue 2 https://doi.org/10.1088/0953-8984/22/2/022201	journal	December 2009
Higher-accuracy van der Waals density functional Lee, Kyuho; Murray, Éamonn D.; Kong, Lingzhu Physical Review B, Vol. 82, Issue 8 https://doi.org/10.1103/PhysRevB.82.081101	journal	August 2010
High-pressure x-ray study of Cu 2 O and Ag 2 O Werner, A.; Hochheimer, H. D. Physical Review B, Vol. 25, Issue 9 https://doi.org/10.1103/PhysRevB.25.5929	journal	May 1982
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) Neugebauer, Jörg; Scheffler, Matthias Physical Review B, Vol. 46, Issue 24 https://doi.org/10.1103/PhysRevB.46.16067	journal	December 1992
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
Approaching chemical accuracy with density functional calculations: Diatomic energy corrections Grindy, Scott; Meredig, Bryce; Kirklin, Scott Physical Review B, Vol. 87, Issue 7 https://doi.org/10.1103/PhysRevB.87.075150	journal	February 2013
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
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
Theory and Application for the Scanning Tunneling Microscope Tersoff, J.; Hamann, D. R. Physical Review Letters, Vol. 50, Issue 25 https://doi.org/10.1103/PhysRevLett.50.1998	journal	June 1983
Bethe-Salpeter equation calculations of core excitation spectra Vinson, J.; Rehr, J. J.; Kas, J. J. Physical Review B, Vol. 83, Issue 11 https://doi.org/10.1103/PhysRevB.83.115106	journal	March 2011
Efficient implementation of core-excitation Bethe–Salpeter equation calculations Gilmore, K.; Vinson, John; Shirley, E. L. Computer Physics Communications, Vol. 197 https://doi.org/10.1016/j.cpc.2015.08.014	journal	December 2015
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
First-principles computation of material properties: the ABINIT software project Gonze, X.; Beuken, J. -M.; Caracas, R. Computational Materials Science, Vol. 25, Issue 3 https://doi.org/10.1016/S0927-0256(02)00325-7	journal	November 2002
Optimized pseudopotentials Rappe, Andrew M.; Rabe, Karin M.; Kaxiras, Efthimios Physical Review B, Vol. 41, Issue 2 https://doi.org/10.1103/PhysRevB.41.1227	journal	January 1990
Thermodynamic stability and structure of copper oxide surfaces: A first-principles investigation Soon, Aloysius; Todorova, Mira; Delley, Bernard Physical Review B, Vol. 75, Issue 12 https://doi.org/10.1103/PhysRevB.75.125420	journal	March 2007
Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications Pan, Xiaoyang; Yang, Min-Quan; Fu, Xianzhi Nanoscale, Vol. 5, Issue 9 https://doi.org/10.1039/c3nr00476g	journal	January 2013
Density functional study of oxygen on Cu(100) and Cu(110) surfaces Duan, X.; Warschkow, O.; Soon, A. Physical Review B, Vol. 81, Issue 7 https://doi.org/10.1103/PhysRevB.81.075430	journal	February 2010
Formation enthalpies by mixing GGA and GGA + U calculations Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045115	journal	July 2011
Effect of Nature and Location of Defects on Bandgap Narrowing in Black TiO ₂ Nanoparticles Naldoni, Alberto; Allieta, Mattia; Santangelo, Saveria Journal of the American Chemical Society, Vol. 134, Issue 18 https://doi.org/10.1021/ja3012676	journal	April 2012
TiO2-based Photocatalysis: Surface Defects, Oxygen and Charge Transfer Thompson, Tracy L.; Yates, John T. Topics in Catalysis, Vol. 35, Issue 3-4 https://doi.org/10.1007/s11244-005-3825-1	journal	July 2005
Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation Grabow, L. C.; Mavrikakis, M. ACS Catalysis, Vol. 1, Issue 4 https://doi.org/10.1021/cs200055d	journal	February 2011
Copper(I)-Based p -Type Oxides for Photoelectrochemical and Photovoltaic Solar Energy Conversion Sullivan, Ian; Zoellner, Brandon; Maggard, Paul A. Chemistry of Materials, Vol. 28, Issue 17 https://doi.org/10.1021/acs.chemmater.6b00926	journal	August 2016
The Surface Structure of Cu ₂ O(100) Soldemo, Markus; Stenlid, Joakim Halldin; Besharat, Zahra The Journal of Physical Chemistry C, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcc.5b11350	journal	February 2016
A hard X-ray nanoprobe beamline for nanoscale microscopy Winarski, Robert P.; Holt, Martin V.; Rose, Volker Journal of Synchrotron Radiation, Vol. 19, Issue 6 https://doi.org/10.1107/S0909049512036783	journal	September 2012
X-Ray Absorption Spectra of Water from First Principles Calculations Prendergast, David; Galli, Giulia Physical Review Letters, Vol. 96, Issue 21 https://doi.org/10.1103/PhysRevLett.96.215502	journal	May 2006
X-ray spectroscopy as a probe for lithium polysulfide radicals Pascal, Tod A.; Pemmaraju, C. D.; Prendergast, David Physical Chemistry Chemical Physics, Vol. 17, Issue 12 https://doi.org/10.1039/C4CP05316H	journal	January 2015
Calculations of near-edge x-ray-absorption spectra of gas-phase and chemisorbed molecules by means of density-functional and transition-potential theory Triguero, L.; Pettersson, L. G. M.; Ågren, H. Physical Review B, Vol. 58, Issue 12 https://doi.org/10.1103/PhysRevB.58.8097	journal	September 1998
L 2 , 3 x-ray-absorption edges of d 0 compounds: K + , Ca 2 + , Sc 3 + , and Ti 4 + in O h (octahedral) symmetry de Groot, F. M. F.; Fuggle, J. C.; Thole, B. T. Physical Review B, Vol. 41, Issue 2 https://doi.org/10.1103/PhysRevB.41.928	journal	January 1990
X-ray absorption near-edge spectroscopy in bioinorganic chemistry: Application to M–O2 systems Sarangi, Ritimukta Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.06.024	journal	January 2013
XSEDE: Accelerating Scientific Discovery Towns, John; Cockerill, Timothy; Dahan, Maytal Computing in Science & Engineering, Vol. 16, Issue 5 https://doi.org/10.1109/MCSE.2014.80	journal	September 2014
Tailoring Copper Oxide Semiconductor Nanorod Arrays for Photoelectrochemical Reduction of Carbon Dioxide to Methanol Rajeshwar, Krishnan; de Tacconi, Norma R.; Ghadimkhani, Ghazaleh ChemPhysChem, Vol. 14, Issue 10 https://doi.org/10.1002/cphc.201300080	journal	May 2013
Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation Grabow, L. C.; Mavrikakis, M. ACS Catalysis, Vol. 1, Issue 4 https://doi.org/10.1021/cs200055d	journal	February 2011
Density functional theory periodic slab calculations of adsorption and dissociation of H ₂ O on the Cu ₂ O(110):CuO surface Saraireh, Sherin A.; Altarawneh, Mohammednoor Canadian Journal of Physics, Vol. 91, Issue 12 https://doi.org/10.1139/cjp-2013-0272	journal	December 2013

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