TiO2表面光催化水分解和碳氧化物氧化还原的第一性原理研究

在太阳光照射下利用催化剂把水或二氧化碳转化为氢气、甲醇等燃料是一种有潜力的将太阳能转化为化学能的方法，有希望解决当前受到极大关注的能源和环境问题。低转化效率是光催化技术目前面临的普遍问题，阻碍了其实际应用。对光化学反应基本过程的深入理解有助于发现影响效率的原因，从而促进对现有催化剂的改进以及新催化剂的开发和设计。在这里，我们采用基于密度泛函理论的第一性原理计算方法，以金红石型二氧化钛（TiO₂）为模型催化剂，对光解水、二氧化碳还原和一氧化碳氧化这三个重要光催化过程的反应机理进行了原子尺度的详细研究，以期深化对这些反应的理解。

对金红石型TiO₂(110)表面的光解水产氧（OER）过程进行了详细的研究。我们提出了一个更全面的OER图像，包括了以前未报道过的涉及催化剂面内氧的反应路径，其中每个基元反应步骤的能量变化和相应的势垒通过高精度的杂化泛函HSE06给出。对电子结构的分析表明反应过程中形成的各种氧和羟基链会从其周围吸收不同数量的电荷。这种属性决定了是否需要光激发空穴来完成某个基元反应步骤；即，有了光生空穴，该步骤从吸热变为放热。这些反应路径中每个基元步骤均为放热反应，并且相应的活化能很小。这表明OER在这个表面很容易进行，光生载流子的产生、分离和传输可能是提高效率的关键。

对金红石型TiO₂(110)面的光诱导的CO₂活化进行了研究。目前，将CO₂光催化还原为具有附加值的化学品或燃料的效率仍然较低，惰性分子CO₂的初始活化被认为是制约效率的关键因素之一。在TiO₂表面，大家通常认为CO₂通过从催化剂表面接收一个光生电子形成弯曲的CO₂ ^-自由基，或者接受两个电子和一个质子形成HCOO^-阴离子来进行活化。这里，我们发现了一种新的光诱导活化机制：当活性位点附近同时存在两个光生电子时，CO₂直接裂解为CO分子和一个吸附的O^2-阴离子。与之前提出的反应路径相比，这条路径在热力学和动力学上更有利。我们的结果加深了对CO₂光诱导活化的理解，并指出催化剂表面光生电子浓度不足是CO₂光催化还原效率低下的一个可能原因。

此外，我们还研究了金红石型TiO₂(110)面的CO光催化氧化过程。与光解水和CO₂光催化还原等反应不同，CO的光催化氧化是一种放热反应，无需将太阳能转换成产物中的键能。此反应通常被认为始于O₂在催化剂表面氧空位处的吸附和活化，然后O₂中的一个O与CO结合生成CO₂。因此，一个有缺陷的表面是不可缺少的。然而，该路径并非可持续的催化过程，因为氧空位会被反应后剩余的O填充。这里我们揭示了一种新的机理，其中CO的光氧化可以在无缺陷表面上持续进行。有趣的是，对整个过程中的电荷分析表明空穴在反应中起着催化剂的作用，它显著降低了反应的活化能，并在一个完整的催化循环后仍未被消耗。因此，通过p型掺杂的方式来提供空穴是一种有潜力的设计催化剂的策略。我们的研究不仅加深了人们对CO光氧化的理解，还有助于解析其他放热光催化反应。

[1] GRAY H B. Powering the planet with solar fuel [J]. Nature Chemistry, 2009,1(1): 7.
[2] ZüTTEL A, REMHOF A, BORGSCHULTE A, et al. Hydrogen: the futureenergy carrier [J]. Philosophical Transactions of the Royal Society A:Mathematical, Physical and Engineering Sciences, 2010, 368(1923):3329-3342.
[3] BALZANI V, CREDI A, VENTURI M. Photochemical conversion of solarenergy [J]. ChemSusChem: Chemistry & Sustainability Energy & Materials,2008, 1(1-2): 26-58.
[4] CHEN X, SHEN S, GUO L, et al. Semiconductor-based photocatalytichydrogen generation [J]. Chemical Reviews, 2010, 110(11): 6503-6570.
[5] CHRISTOFORIDIS K C, FORNASIERO P. Photocatalytic hydrogenproduction: a rift into the future energy supply [J]. ChemCatChem, 2017, 9(9):1523-1544.
[6] SCHNEIDER J, MATSUOKA M, TAKEUCHI M, et al. Understanding TiO2photocatalysis: mechanisms and materials [J]. Chemical Reviews, 2014,114(19): 9919-9986.
[7] PINAUD B A, BENCK J D, SEITZ L C, et al. Technical and economicfeasibility of centralized facilities for solar hydrogen production viaphotocatalysis and photoelectrochemistry [J]. Energy & EnvironmentalScience, 2013, 6(7): 1983-2002.
[8] FABIAN D M, HU S, SINGH N, et al. Particle suspension reactors andmaterials for solar-driven water splitting [J]. Energy & EnvironmentalScience, 2015, 8(10): 2825-2850.
[9] KANG U, CHOI S K, HAM D J, et al. Photosynthesis of formate from CO2and water at 1% energy efficiency via copper iron oxide catalysis [J]. Energy& Environmental Science, 2015, 8(9): 2638-2643.
[10] CHEN S, TAKATA T, DOMEN K. Particulate photocatalysts for overall watersplitting [J]. Nature Reviews Materials, 2017, 2(10): 1-17.
[11] FUJISHIMA A, HONDA K. Electrochemical photolysis of water at asemiconductor electrode [J]. Nature, 1972, 238(5358): 37-38.
[12] WANG Q, HISATOMI T, JIA Q, et al. Scalable water splitting on particulatephotocatalyst sheets with a solar-to-hydrogen energy conversion efficiencyexceeding 1% [J]. Nature Materials, 2016, 15(6): 611-615.
[13] PAN C, TAKATA T, NAKABAYASHI M, et al. A complex perovskite-typeoxynitride: the first photocatalyst for water splitting operable at up to 600 nm[J]. Angewandte Chemie International Edition, 2015, 54(10): 2955-2959.
[14] MAEDA K, TAKATA T, HARA M, et al. GaN: ZnO solid solution as aphotocatalyst for visible-light-driven overall water splitting [J]. Journal of theAmerican Chemical Society, 2005, 127(23): 8286-8287.
[15] MARTIN D J, REARDON P J T, MONIZ S J, et al. Visible light-driven purewater splitting by a nature-inspired organic semiconductor-based system [J].Journal of the American Chemical Society, 2014, 136(36): 12568-12571.
[16] HE F, CHEN G, YU Y, et al. Facile approach to synthesize g-PAN/g-C3N4composites with enhanced photocatalytic H2 evolution activity [J]. ACSApplied Materials & Interfaces, 2014, 6(10): 7171-7179.
[17] SCHWINGHAMMER K, MESCH M B, DUPPEL V, et al. Crystalline carbonnitride nanosheets for improved visible-light hydrogen evolution [J]. Journalof the American Chemical Society, 2014, 136(5): 1730-7133.
[18] MARSCHALL R. Semiconductor composites: strategies for enhancing chargecarrier separation to improve photocatalytic activity [J]. Advanced FunctionalMaterials, 2014, 24(17): 2421-40.
[19] ZHANG X, YU L, ZHUANG C, et al. Highly asymmetric phthalocyanine as asensitizer of graphitic carbon nitride for extremely efficient photocatalytic H2production under near-infrared light [J]. ACS Catalysis, 2014, 4(1): 162-170.
[20] LIU J, LIU Y, LIU N, et al. Metal-free efficient photocatalyst for stablevisible water splitting via a two-electron pathway [J]. Science, 2015,347(6225): 970-974.
[21] FUJISHIMA A, ZHANG X, TRYK D A. TiO2 photocatalysis and relatedsurface phenomena [J]. Surface Science Reports, 2008, 63(12): 515-582.
[22] CHOI W, TERMIN A, HOFFMANN M R. The role of metal ion dopants inquantum-sized TiO2: correlation between photoreactivity and charge carrierrecombination dynamics [J]. The Journal of Physical Chemistry, 2002, 98(51):13669-13679.
[23] CHOI W, TERMIN A, HOFFMANN M R. Einfl ü sse vondotierungs-metall-ionen auf die photokatalytische reaktivität vonTiO2-Quantenteilchen [J]. Angewandte Chemie, 1994, 106(10): 1148-1149.
[24] MARTIN S T, MORRISON C L, HOFFMANN M R. Photochemicalmechanism of size-quantized vanadium-doped TiO2 particles [J]. The Journalof Physical Chemistry, 1994, 98(51): 13695-704.
[25] WANG Y, HAO Y, CHENG H, et al. The photoelectrochemistry of transitionmetal-ion-doped TiO2 nanocrystalline electrodes and higher solar cellconversion efficiency based on Zn2+-doped TiO2 electrode [J]. Journal ofMaterials Science, 1999, 34(12): 2773-2779.
[26] WANG J, TAFEN D N, LEWIS J P, et al. Origin of photocatalytic activity ofnitrogen-doped TiO2 nanobelts [J]. Journal of the American Chemical Society,2009, 131(34): 12290-12297.
[27] WANG C-Y, BAHNEMANN D W, DOHRMANN J K. A novel preparation ofiron-doped TiO2 nanoparticles with enhanced photocatalytic activity [J].Chemical Communications, 2000, (16): 1539-1540.
[28] HAMEDANI H A, ALLAM N K, GARMESTANI H, et al. Electrochemicalfabrication of strontium-doped TiO2 nanotube array electrodes andinvestigation of their photoelectrochemical properties [J]. The Journal ofPhysical Chemistry C, 2011, 115(27): 13480-13486.
[29] ASAHI R, MORIKAWA T, OHWAKI T, et al. Visible-light photocatalysis innitrogen-doped titanium oxides [J]. Science, 2001, 293(5528): 269-271.
[30] BURDA C, LOU Y, CHEN X, et al. Enhanced nitrogen doping in TiO2nanoparticles [J]. Nano Letters, 2003, 3(8): 1049-1051.
[31] UMEBAYASHI T, YAMAKI T, YAMAMOTO S, et al. Sulfur-doping ofrutile-titanium dioxide by ion implantation: photocurrent spectroscopy andfirst-principles band calculation studies [J]. Journal of Applied Physics, 2003,93(9): 5156-5160.
[32] UMEBAYASHI T, YAMAKI T, ITOH H, et al. Band gap narrowing oftitanium dioxide by sulfur doping [J]. Applied physics letters, 2002, 81(3):454-456.
[33] IRIE H, WATANABE Y, HASHIMOTO K. Nitrogen-concentrationdependence on photocatalytic activity of TiO2-xNx powders [J]. The Journal ofPhysical Chemistry B, 2003, 107(23): 5483-5486.
[34] LI D, HANEDA H, LABHSETWAR N K, et al. Visible-light-drivenphotocatalysis on fluorine-doped TiO2 powders by the creation of surfaceoxygen vacancies [J]. Chemical Physics Letters, 2005, 401(4-6): 579-584.
[35] HAMILTON J W, BYRNE J A, DUNLOP P S, et al. Evaluating themechanism of visible light activity for N, F-TiO2 using photoelectrochemistry[J]. The Journal of Physical Chemistry C, 2014, 118(23): 12206-12215.
[36] LUO H, TAKATA T, LEE Y, et al. Photocatalytic activity enhancing fortitanium dioxide by co-doping with bromine and chlorine [J]. Chemistry ofMaterials, 2004, 16(5): 846-849.
[37] ZHANG Q, GAO T, ANDINO J M, et al. Copper and iodine co-modified TiO2 nanoparticles for improved activity of CO2 photoreduction with water vapor[J]. Applied Catalysis B: Environmental, 2012, 123: 257-264.
[38] ZHANG J, XI J, JI Z. Mo+N codoped TiO2 sheets with dominant {001} facetsfor enhancing visible-light photocatalytic activity [J]. Journal of MaterialsChemistry, 2012, 22(34): 17700-17708.
[39] DONG B-B, ZHANG B-B, WU H-Y, et al. Synthesis, characterization andcatalytic evaluation of SBA-15 supported 12-tungstophosphoric acidmesoporous materials in the oxidation of benzaldehyde to benzoic acid [J].Materials Research Bulletin, 2013, 48(7): 2491-2496.
[40] WU X, YIN S, DONG Q, et al. Photocatalytic properties of Nd and Ccodoped TiO2 with the whole range of visible light absorption [J]. The Journalof Physical Chemistry C, 2013, 117(16): 8345-8352.
[41] YAN C, YI W, YUAN H, et al. A highly photoactive S, Cu-codopednano-TiO2 photocatalyst: Synthesis and characterization for enhancedphotocatalytic degradation of neutral red [J]. Environmental Progress &Sustainable Energy, 2014, 33(2): 419-429.
[42] ZHANG M, WU J, HOU J, et al. Molybdenum and nitrogen co-dopedtitanium dioxide nanotube arrays with enhanced visible light photocatalyticactivity [J]. Science of Advanced Materials, 2013, 5(6): 535-541.
[43] CHEN X, LIU L, YU P Y, et al. Increasing solar absorption for photocatalysiswith black hydrogenated titanium dioxide nanocrystals [J]. Science, 2011,331(6018): 746-750.
[44] LIU M, CHEN Y, SU J, et al. Photocatalytic hydrogen production usingtwinned nanocrystals and an unanchored NiSx co-catalyst [J]. Nature Energy,2016, 1(11): 1-8.
[45] RAN J, ZHANG J, YU J, et al. Earth-abundant cocatalysts forsemiconductor-based photocatalytic water splitting [J]. Chemical SocietyReviews, 2014, 43(22): 7787-7812.
[46] ZHANG J, XU Q, FENG Z, et al. Importance of the relationship betweensurface phases and photocatalytic activity of TiO2 [J]. Angewandte ChemieInternational Edition, 2008, 120(9): 1790-1793.
[47] WANG X, XU Q, LI M, et al. Photocatalytic overall water splitting promotedby an α-β phase junction on Ga2O3 [J]. Angewandte Chemie InternationalEdition, 2012, 124(52): 13266-13269.
[48] MONIZ S J, SHEVLIN S A, MARTIN D J, et al. Visible-light drivenheterojunction photocatalysts for water splitting–a critical review [J]. Energy& Environmental Science, 2015, 8(3): 731-759.
[49] WANG H, ZHANG L, CHEN Z, et al. Semiconductor heterojunctionphotocatalysts: design, construction, and photocatalytic performances [J].Chemical Society Reviews, 2014, 43(15): 5234-5244.
[50] LI R, ZHANG F, WANG D, et al. Spatial separation of photogeneratedelectrons and holes among {010} and {110} crystal facets of BiVO4 [J].Nature Communications, 2013, 4(1): 1-7.
[51] LIU G, YANG H G, PAN J, et al. Titanium dioxide crystals with tailoredfacets [J]. Chemical Reviews, 2014, 114(19): 9559-9612.
[52] YANG Y, GU J, YOUNG J L, et al. Semiconductor interfacial carrierdynamics via photoinduced electric fields [J]. Science, 2015, 350(6264):1061-1065.
[53] ABDI F F, HAN L, SMETS A H, et al. Efficient solar water splitting byenhanced charge separation in a bismuth vanadate-silicon tandemphotoelectrode [J]. Nature Communications, 2013, 4(1): 1-7.
[54] CHEN R, PANG S, AN H, et al. Charge separation via asymmetricillumination in photocatalytic Cu2O particles [J]. Nature Energy, 2018, 3(8):655-663.
[55] NAKAMURA R, NAKATO Y. Primary intermediates of oxygenphotoevolution reaction on TiO2 (rutile) particles, revealed by in situ FTIRabsorption and photoluminescence measurements [J]. Journal of the AmericanChemical Society, 2004, 126(4): 1290-1298.
[56] NAKAMURA R, OKAMURA T, OHASHI N, et al. Molecular mechanisms ofphotoinduced oxygen evolution, PL emission, and surface roughening atatomically smooth (110) and (100) n-TiO2 (rutile) surfaces in aqueous acidicsolutions [J]. Journal of the American Chemical Society, 2005, 127(37):12975-12983.
[57] IMANISHI A, OKAMURA T, OHASHI N, et al. Mechanism of waterphotooxidation reaction at atomically flat TiO2 (rutile) (110) and (100)surfaces: dependence on solution pH [J]. Journal of the American ChemicalSociety, 2007, 129(37): 11569-11578.
[58] VALDES A, QU Z-W, KROES G-J, et al. Oxidation and photo-oxidation ofwater on TiO2 surface [J]. The Journal of Physical Chemistry C, 2008,112(26): 9872-9879.
[59] TANG J, DURRANT J R, KLUG D R. Mechanism of photocatalytic watersplitting in TiO2. Reaction of water with photoholes, importance of chargecarrier dynamics, and evidence for four-hole chemistry [J]. Journal of theAmerican Chemical Society, 2008, 130(42): 13885-13891.
[60] TAN S, FENG H, JI Y, et al. Observation of photocatalytic dissociation ofwater on terminal Ti sites of TiO2(110)-1×1 surface [J]. Journal of theAmerican Chemical Society, 2012, 134(24): 9978-9985.
[61] LEE J, SORESCU D C, DENG X, et al. Water chain formation on TiO2(110)[J]. The Journal of Physical Chemistry Letters, 2012, 4(1): 53-57.
[62] YANG W, WEI D, JIN X, et al. Effect of the hydrogen bond in photoinducedwater dissociation: A double-edged sword [J]. The Journal of PhysicalChemistry Letters, 2016, 7(4): 603-608.
[63] LI Y-F, SELLONI A. Pathway of photocatalytic oxygen evolution on aqueousTiO2 anatase and insights into the different activities of anatase and rutile [J].ACS Catalysis, 2016, 6(7): 4769-4774.
[64] CHEN J, LI Y-F, SIT P, et al. Chemical dynamics of the first proton-coupledelectron transfer of water oxidation on TiO2 anatase [J]. Journal of theAmerican Chemical Society, 2013, 135(50): 18774-18777.
[65] WANG D, SHENG T, CHEN J, et al. Identifying the key obstacle inphotocatalytic oxygen evolution on rutile TiO2 [J]. Nature Catalysis, 2018,1(4): 291-299.
[66] LI Z, TIAN B, ZHEN W, et al. Inhibition of hydrogen and oxygenrecombination using oxygen transfer reagent hemin chloride in Pt/TiO2dispersion for photocatalytic hydrogen generation [J]. Applied Catalysis B:Environmental, 2017, 203: 408-15.
[67] MONTOYA J, BAHNEMANN D, SALVADOR P, et al. Catalytic role ofbridging oxygens in TiO2 liquid phase photocatalytic reactions: analysis ofH216O photooxidation on labeled Ti18O2 [J]. Catalysis Science & Technology,2017, 7(4): 902-910.
[68] ZHANG H, BANFIELD J F. Understanding polymorphic phasetransformation behavior during growth of nanocrystalline aggregates: insightsfrom TiO2 [J]. The Journal of Physical Chemistry B, 2000, 104(15):3481-3487.
[69] RANADE M, NAVROTSKY A, ZHANG H, et al. Energetics ofnanocrystalline TiO2 [J]. Proceedings of the National Academy of Sciences,2002, 99(suppl 2): 6476-6481.
[70] SHKLOVER V, NAZEERUDDIN M K, SAKEERUDDIN S, et al. Structureof nanocrystalline TiO2 powders and precursor to their highly efficientphotosensitizer [J]. Chemistry of Materials, 1997, 9(2): 430-439.
[71] BURNSIDE S, SHKLOVER V, BARBE C, et al. Self-organization of TiO2nanoparticles in thin films [J]. Chemistry of Materials, 1998, 10(9): 2419-2425.
[72] WILSON R. Observation and analysis of surface states on TiO2 electrodes inaqueous electrolytes [J]. Journal of The Electrochemical Society, 1980,127(1): 228-34.
[73] SALVADOR P, GUTIERREZ C. The nature of surface states involved in thephoto- and electroluminescence spectra of n-titanium dioxide electrodes [J].The Journal of Physical Chemistry, 1984, 88(16): 3696-3698.
[74] CHANG X, WANG T, GONG J. CO2 photo-reduction: insights into CO2activation and reaction on surfaces of photocatalysts [J]. Energy &Environmental Science, 2016, 9(7): 2177-2196.
[75] JANG J W, CHO S, MAGESH G, et al. Aqueous-solution route to zinctelluride films for application to CO2 reduction [J]. Angewandte ChemieInternational Edition, 2014, 53(23): 5852-5857.
[76] JANG Y J, JANG J-W, LEE J, et al. Selective CO production by Au coupledZnTe/ZnO in the photoelectrochemical CO2 reduction system [J]. Energy &Environmental Science, 2015, 8(12): 3597-3604.
[77] LIN J, PAN Z, WANG X. Photochemical reduction of CO2 by graphiticcarbon nitride polymers [J]. ACS Sustainable Chemistry & Engineering, 2014,2(3): 353-358.
[78] YU J, WANG K, XIAO W, et al. Photocatalytic reduction of CO2 intohydrocarbon solar fuels over gC3N4-Pt nanocomposite photocatalysts [J].Physical Chemistry Chemical Physics, 2014, 16(23): 11492-11501.
[79] XIE S, ZHANG Q, LIU G, et al. Photocatalytic and photoelectrocatalyticreduction of CO2 using heterogeneous catalysts with controllednanostructures [J]. Chemical Communications, 2016, 52(1): 35-59.
[80] KUMAR B, LLORENTE M, FROEHLICH J, et al. Photochemical andphotoelectrochemical reduction of CO2 [J]. Annual Review of PhysicalChemistry, 2012, 63(1): 541-569.
[81] HONG J, ZHANG W, REN J, et al. Photocatalytic reduction of CO2: a briefreview on product analysis and systematic methods [J]. Analytical Methods,2013, 5(5): 1086-1097.
[82] LI X, WEN J, LOW J, et al. Design and fabrication of semiconductorphotocatalyst for photocatalytic reduction of CO2 to solar fuel [J]. ScienceChina Materials, 2014, 57(1): 70-100.
[83] TU W, ZHOU Y, ZOU Z. Photocatalytic conversion of CO2 into renewablehydrocarbon fuels: state-of-the-art accomplishment, challenges, and prospects[J]. Advanced Materials, 2014, 26(27): 4607-4626.
[84] NGUYEN T-V, WU J C, CHIOU C-H. Photoreduction of CO2 overRuthenium dye-sensitized TiO2-based catalysts under concentrated naturalsunlight [J]. Catalysis Communications, 2008, 9(10): 2073-2076.
[85] WANG C, THOMPSON R L, BALTRUS J, et al. Visible light photoreductionof CO2 using CdSe/Pt/TiO2 heterostructured catalysts [J]. The Journal ofPhysical Chemistry Letters, 2010, 1(1): 48-53.
[86] CAO L, SAHU S, ANILKUMAR P, et al. Carbon nanoparticles asvisible-light photocatalysts for efficient CO2 conversion and beyond [J].Journal of the American Chemical Society, 2011, 133(13): 4754-4757.
[87] WANG C, THOMPSON R L, OHODNICKI P, et al. Size-dependentphotocatalytic reduction of CO2 with PbS quantum dot sensitized TiO2heterostructured photocatalysts [J]. Journal of Materials Chemistry, 2011,21(35): 13452-13457.
[88] TSAI C-W, CHEN H M, LIU R-S, et al. Ni@NiO core-shellstructure-modified nitrogen-doped InTaO4 for solar-driven highly efficientCO2 reduction to methanol [J]. The Journal of Physical Chemistry C, 2011,115(20): 10180-10186.
[89] ZHANG Q, LI Y, ACKERMAN E A, et al. Visible light responsiveiodine-doped TiO2 for photocatalytic reduction of CO2 to fuels [J]. AppliedCatalysis A: General, 2011, 400(1-2): 195-202.
[90] RICHARDSON P, PERDIGOTO M L, WANG W, et al. RETRACTED:manganese-and copper-doped titania nanocomposites for the photocatalyticreduction of carbon dioxide into methanol [Z]. Elsevier. 2012
[91] HOU W, HUNG W, PAVASKAR P, et al. Photocatalytic conversion of CO2 tohydrocarbon fuels via plasmon-enhanced absorption and metallic interbandtransitions. ACS Catalysis, 2011, 1(8): 929-936.
[92] TU W, ZHOU Y, LI H, et al. Au@TiO2 yolk–shell hollow spheres forplasmon-induced photocatalytic reduction of CO2 to solar fuel via a localelectromagnetic field [J]. Nanoscale, 2015, 7(34): 14232-14236.
[93] ZHANG Z, WANG Z, CAO S-W, et al. Au/Pt nanoparticle-decorated TiO2nanofibers with plasmon-enhanced photocatalytic activities for solar-to-fuelconversion [J]. The Journal of Physical Chemistry C, 2013, 117(49):25939-25947.
[94] LIU Y, HUANG B, DAI Y, et al. Selective ethanol formation fromphotocatalytic reduction of carbon dioxide in water with BiVO4 photocatalyst[J]. Catalysis Communications, 2009, 11(3): 210-213.
[95] MAO J, PENG T, ZHANG X, et al. Selective methanol production from photocatalytic reduction of CO2 on BiVO4 under visible light irradiation [J].Catalysis Communications, 2012, 28: 38-41.
[96] BA X, YAN L-L, HUANG S, et al. New way for CO2 reduction under visiblelight by a combination of a Cu electrode and semiconductor thin film: Cu2Oconduction type and morphology effect [J]. The Journal of PhysicalChemistry C, 2014, 118(42): 24467-24478.
[97] SCHREIER M, GAO P, MAYER M T, et al. Efficient and selective carbondioxide reduction on low cost protected Cu2O photocathodes using amolecular catalyst [J]. Energy & Environmental Science, 2015, 8(3):855-861.
[98] PAN P-W, CHEN Y-W. Photocatalytic reduction of carbon dioxide onNiO/InTaO4 under visible light irradiation [J]. Catalysis Communications,2007, 8(10): 1546-1549.
[99] GU J, WUTTIG A, KRIZAN J W, et al. Mg-doped CuFeO2 photocathodes forphotoelectrochemical reduction of carbon dioxide [J]. The Journal of PhysicalChemistry C, 2013, 117(24): 12415-12422.
[100] YU J, LOW J, XIAO W, et al. Enhanced photocatalytic CO2-reductionactivity of anatase TiO2 by coexposed {001} and {101} facets [J]. Journal ofthe American Chemical Society, 2014, 136(25): 8839-8842.
[101] LI P, ZHOU Y, ZHAO Z, et al. Hexahedron prism-anchored octahedronalCeO2: crystal facet-based homojunction promoting efficient solar fuelsynthesis [J]. Journal of the American Chemical Society, 2015, 137(30):9547-9550.
[102] LI G, CISTON S, SAPONJIC Z V, et al. Synthesizing mixed-phase TiO2nanocomposites using a hydrothermal method for photo-oxidation andphotoreduction applications [J]. Journal of Catalysis, 2008, 253(1): 105-110.
[103] LI P, XU H, LIU L, et al. Constructing cubic-orthorhombic surface-phasejunctions of NaNbO3 towards significant enhancement of CO2 photoreduction[J]. Journal of Materials Chemistry A, 2014, 2(16): 5606-5609.
[104] TU W, ZHOU Y, LIU Q, et al. Robust hollow spheres consisting of alternatingtitania nanosheets and graphene nanosheets with high photocatalytic activityfor CO2 conversion into renewable fuels [J]. Advanced Functional Materials,2012, 22(6): 1215-1221.
[105] SHI H, CHEN G, ZHANG C, et al. Polymeric g-C3N4 coupled with NaNbO3nanowires toward enhanced photocatalytic reduction of CO2 into renewablefuel [J]. ACS Catalysis, 2014, 4(10): 3637-3643.
[106] CAO S-W, LIU X-F, YUAN Y-P, et al. Solar-to-fuels conversion over In2O3/g-C3N4 hybrid photocatalysts [J]. Applied Catalysis B: Environmental,2014, 147: 940-946.
[107] AN X, LI K, TANG J. Cu2O/reduced graphene oxide composites for thephotocatalytic conversion of CO2 [J]. ChemSusChem, 2014, 7(4): 1086-1093.
[108] KOČí K, OBALOVá L, MATĚJOVá L, et al. Effect of TiO2 particle size onthe photocatalytic reduction of CO2 [J]. Applied Catalysis B: Environmental,2009, 89(3-4): 494-502.
[109] LIU Q, ZHOU Y, KOU J, et al. High-yield synthesis of ultralong and ultrathinZn2GeO4 nanoribbons toward improved photocatalytic reduction of CO2 intorenewable hydrocarbon fuel [J]. Journal of the American Chemical Society,2010, 132(41): 14385-14387.
[110] ZHANG X, HAN F, SHI B, et al. Photocatalytic conversion of diluted CO2into light hydrocarbons using periodically modulated multiwalled nanotubearrays [J]. Angewandte Chemie International Edition, 2012, 51(51):12732-12735.
[111] YAN S, WANG J, GAO H, et al. An Ion-Exchange Phase Transformation toZnGa2O4 Nanocube Towards Efficient Solar Fuel Synthesis [J]. AdvancedFunctional Materials, 2013, 23(6): 758-763.
[112] HABISREUTINGER S N, SCHMIDT‐MENDE L, STOLARCZYK J K.Photocatalytic reduction of CO2 on TiO2 and other semiconductors [J].Angewandte Chemie International Edition, 2013, 52(29): 7372-7408.
[113] FREUND H-J, ROBERTS M W. Surface chemistry of carbon dioxide [J].Surface Science Reports, 1996, 25(8): 225-273.
[114] SONG C. Global challenges and strategies for control, conversion andutilization of CO2 for sustainable development involving energy, catalysis,adsorption and chemical processing [J]. Catalysis Today, 2006, 115(1-4):2-32.
[115] SURDHAR P S, MEZYK S P, ARMSTRONG D A. Reduction potential of thecarboxyl radical anion in aqueous solutions [J]. The Journal of PhysicalChemistry, 1989, 93(8): 3360-3363.
[116] ROSEN B A, SALEHI-KHOJIN A, THORSON M R, et al. Ionicliquid-mediated selective conversion of CO2 to CO at low overpotentials [J].Science, 2011, 334(6056): 643-644.
[117] SCHWARZ H, DODSON R. Reduction potentials of CO2- and the alcoholradicals [J]. The Journal of Physical Chemistry, 1989, 93(1): 409-414.
[118] BENSON E E, KUBIAK C P, SATHRUM A J, et al. Electrocatalytic andhomogeneous approaches to conversion of CO2 to liquid fuels [J]. Chemical Society Reviews, 2009, 38(1): 89-99.
[119] LI W. Electrocatalytic reduction of CO2 to small organic molecule fuels onmetal catalysts [M]. Advances in CO2 conversion and utilization. ACSPublications. 2010: 55-76.
[120] INOUE T, FUJISHIMA A, KONISHI S, et al. Photoelectrocatalytic reductionof carbon dioxide in aqueous suspensions of semiconductor powders [J].Nature, 1979, 277(5698): 637-638.
[121] HUYNH M H V, MEYER T J. Proton-coupled electron transfer [J]. ChemicalReviews, 2007, 107(11): 5004-5064.
[122] COSTENTIN C, ROBERT M, SAVéANT J-M. Catalysis of theelectrochemical reduction of carbon dioxide [J]. Chemical Society Reviews,2013, 42(6): 2423-2436.
[123] WHITE J L, BARUCH M F, PANDER III J E, et al. Light-drivenheterogeneous reduction of carbon dioxide: photocatalysts andphotoelectrodes [J]. Chemical Reviews, 2015, 115(23): 12888-12935.
[124] HARA K, KUDO A, SAKATA T, et al. High efficiency electrochemicalreduction of carbon dioxide under high pressure on a gas diffusion electrodecontaining Pt catalysts [J]. Journal of the Electrochemical Society, 1995,142(4): L57-L59.
[125] YIN W-J, WEN B, BANDARU S, et al. The effect of excess electron and holeon CO2 adsorption and activation on rutile (110) surface [J]. ScientificReports, 2016, 6(1): 1-9.
[126] JI Y, LUO Y. Theoretical Study on the Mechanism of Photoreduction of CO2to CH4 on the Anatase TiO2 (101) Surface [J]. ACS Catalysis, 2016, 6(3):2018-2025.
[127] JI Y, LUO Y. New mechanism for photocatalytic reduction of CO2 on theanatase TiO2(101) surface: the essential role of oxygen vacancy [J]. Journal ofthe American Chemical Society, 2016, 138(49): 15896-15902.
[128] WU X, LANG J, SUN Z, et al. Photocatalytic conversion of carbon monoxide:from pollutant removal to fuel production [J]. Applied Catalysis B:Environmental, 2021, 295: 120312.
[129] CHEN B-H, CLOSE J, WHITE J. The role of ultraviolet radiation inpromoting the palladium-catalyzed oxidation of carbon monoxide [J]. Journalof Catalysis, 1977, 46(3): 253-258.
[130] TRIPA C E, ARUMANINAYAGAM C R, YATES JR J T. Kineticsmeasurements of CO photo-oxidation on Pt(111) [J]. The Journal of ChemicalPhysics, 1996, 105(4): 1691-1696.
[131] KAO F-J, BUSCH D, DA COSTA D G, et al. Femtosecond versusnanosecond surface photochemistry: O2+CO on Pt(111) at 80 K [J]. PhysicalReview Letters, 1993, 70(26): 4098.
[132] MIEHER W, HO W. Bimolecular surface photochemistry: mechanisms of COoxidation on Pt(111) at 85 k [J]. The Journal of Chemical Physics, 1993,99(11): 9279-9295.
[133] SASTRE F, OTERI M, CORMA A, et al. Photocatalytic water gas shift usingvisible or simulated solar light for the efficient, room-temperature hydrogengeneration [J]. Energy & Environmental Science, 2013, 6(7): 2211-2215.
[134] WU X, LANG J, JIANG Y, et al. Thermo-photo catalysis for methanolsynthesis from syngas [J]. ACS Sustainable Chemistry & Engineering, 2019,7(23): 19277-19285.
[135] WANG Y, XIA Q. Fischer-Tropsch synthesis steps into the solar era: lowerolefins from syngas [J]. Chem, 2018, 4(12): 2741-2743.
[136] SASTRE F, CORMA A, GARC í A H. Visible-Light PhotocatalyticConversion of Carbon Monoxide to Methane by Nickel (II) Oxide [J].Angewandte Chemie International Edition, 2013, 125(49): 13221-13225.
[137] DOHNáLEK Z, KIM J, BONDARCHUK O, et al. Physisorption of N2, O2,and CO on fully oxidized TiO2(110) [J]. The Journal of Physical Chemistry B,2006, 110(12): 6229-6235.
[138] ZHANG Z, JR J T Y. Electron-mediated CO oxidation on the TiO2(110)surface during electronic excitation [J]. Journal of the American ChemicalSociety, 2010, 132(37): 12804-12807.
[139] PETRIK N G, KIMMEL G A. Off-Normal CO2 Desorption from thePhotooxidation of CO on Reduced TiO2(110) [J]. Journal of PhysicalChemistry Letters, 2010, 1(17): 2508-2513.
[140] PETRIK N G, KIMMEL G A. Multiple Nonthermal Reaction Steps for thePhotooxidation of CO to CO2 on Reduced TiO2(110) [J]. Journal of PhysicalChemistry Letters, 2013, 4(3): 344-349.
[141] YONGFEI, JI, BING, et al. First Principles Study of O2 Adsorption onReduced Rutile TiO2-(110) Surface Under UV Illumination and Its Role onCO Oxidation [J]. The Journal of Physical Chemistry C, 2013, 117(2): 956–961.
[142] KWEON K E, MANOGARAN D, HWANG G S. Synergetic Role ofPhotogenerated Electrons and Holes in the Oxidation of CO to CO2 onReduced TiO2(110): A First-Principles Study [J]. ACS Catalysis, 2014, 4(11):4051-4056.
[143] PILLAY D, HWANG G S. O2-coverage-dependent CO oxidation on reducedTiO2(110): A first principles study [J]. Journal of Chemical Physics, 2006,125(14): 9438.
[144] LINSEBIGLER A, LU G, YATES J T. CO Photooxidation on TiO2(110) [J].The Journal of Physical Chemistry, 1996, 100(16): 6631-6636.
[145] THEVENET A, JUILLET F, TEICHNER S J. Photointeraction on the Surfaceof Titanium Dioxide between Oxygen and Carbon Monoxide [J]. JapaneseJournal of Applied Physics, 1974, 13(S2): 529.
[146] KUDO A, MISEKI Y. Heterogeneous photocatalyst materials for watersplitting [J]. Chemical Society Reviews, 2009, 38(1): 253-278.
[147] WALTER M G, WARREN E L, MCKONE J R, et al. Solar water splittingcells [J]. Chemical Reviews, 2010, 110(11): 6446-6473.
[148] WANG Z, LI C, DOMEN K. Recent developments in heterogeneousphotocatalysts for solar-driven overall water splitting [J]. Chemical SocietyReviews, 2019, 48(7): 2109-2125.
[149] YE S, DING C, LIU M, et al. Water Oxidation Catalysts for ArtificialPhotosynthesis [J]. Adv Mater, 2019, 31(50): 1902069.
[150] TAKATA T, JIANG J, SAKATA Y, et al. Photocatalytic water splitting with aquantum efficiency of almost unity [J]. Nature, 2020, 581(7809): 411-414.
[151] KRESSE G, HAFNER J. Ab initio molecular dynamics for liquid metals [J].Physical Review B, 1993, 47(1): 558.
[152] KRESSE G, HAFNER J. Ab initio molecular-dynamics simulation of theliquid-metal–amorphous-semiconductor transition in germanium [J]. PhysicalReview B, 1994, 49(20): 14251.
[153] KRESSE G, FURTHMüLLER J. Efficiency of ab-initio total energycalculations for metals and semiconductors using a plane-wave basis set [J].Computational Materials Science, 1996, 6(1): 15-50.
[154] KRUKAU A V, VYDROV O A, IZMAYLOV A F, et al. Influence of theexchange screening parameter on the performance of screened hybridfunctionals [J]. The Journal of Chemical Physics, 2006, 125(22): 224106.
[155] HEYD J, SCUSERIA G E, ERNZERHOF M. Hybrid functionals based on ascreened Coulomb potential [J]. The Journal of Chemical Physics, 2003,118(18): 8207-8215.
[156] LANY S, ZUNGER A. Polaronic hole localization and multiple hole bindingof acceptors in oxide wide-gap semiconductors [J]. Physical Review B, 2009,80(8): 085202.
[157] LæGSGAARD J, STOKBRO K. Hole trapping at Al impurities in silica: A challenge for density functional theories [J]. Physical Review Letters, 2001,86(13): 2834.
[158] D’AVEZAC M, CALANDRA M, MAURI F. Density functional theorydescription of hole-trapping in SiO2: A self-interaction-corrected approach [J].Physical Review B, 2005, 71(20): 205210.
[159] DROGHETTI A, PEMMARAJU C, SANVITO S. Predicting d0 magnetism:Self-interaction correction scheme [J]. Physical Review B, 2008, 78(14):140404.
[160] HENKELMAN G, UBERUAGA B P, JóNSSON H. A climbing image nudgedelastic band method for finding saddle points and minimum energy paths [J].The Journal of Chemical Physics, 2000, 113(22): 9901-9904.
[161] HENRICH V E, DRESSELHAUS G, ZEIGER H. Observation ofTwo-Dimensional Phases Associated with Defect States on the Surface ofTiO2 [J]. Physical Review Letters, 1976, 36(22): 1335.
[162] GANDUGLIA-PIROVANO M V, HOFMANN A, SAUER J. Oxygenvacancies in transition metal and rare earth oxides: Current state ofunderstanding and remaining challenges [J]. Surface Science Reports, 2007,62(6): 219-270.
[163] DIEBOLD U. The surface science of titanium dioxide [J]. Surface ScienceReports, 2003, 48(5-8): 53-229.
[164] TANG W, SANVILLE E, HENKELMAN G. A grid-based Bader analysisalgorithm without lattice bias [J]. Journal of Physics: Condensed Matter, 2009,21(8): 084204.
[165] ZHAO W-N, LIU Z-P. Mechanism and active site of photocatalytic watersplitting on titania in aqueous surroundings [J]. Chemical Science, 2014, 5(6):2256-2264.
[166] WENDT S, MATTHIESEN J, SCHAUB R, et al. Formation and splitting ofpaired hydroxyl groups on reduced TiO2(110) [J]. Physical Review Letters,2006, 96(6): 066107.
[167] DU Y, DESKINS N A, ZHANG Z, et al. Two pathways for water interactionwith oxygen adatoms on TiO2(110) [J]. Physical Review Letters, 2009, 102(9):096102.
[168] WANG Z-T, WANG Y-G, MU R, et al. Probing equilibrium of molecular anddeprotonated water on TiO2(110) [J]. Proceedings of the National Academy ofSciences, 2017, 114(8): 1801-1805.
[169] INDRAKANTI V P, KUBICKI J D, SCHOBERT H H. Photoinducedactivation of CO2 on Ti-based heterogeneous catalysts: Current state, chemical physics-based insights and outlook [J]. Energy & EnvironmentalScience, 2009, 2(7): 745-758.
[170] KOVACIC Z, LIKOZAR B, HUS M. Photocatalytic CO2 reduction: A reviewof ab initio mechanism, kinetics, and multiscale modeling simulations [J].ACS Catalysis, 2020, 10(24): 14984-15007.
[171] JIANG Z, XU X, MA Y, et al. Filling metal-organic framework mesoporeswith TiO2 for CO2 photoreduction [J]. Nature, 2020, 586(7830): 549-554.
[172] COMPTON R, REINHARDT P, COOPER C. Collisional ionization of Na, K,and Cs by CO2, COS, and CS2: Molecular electron affinities [J]. The Journalof Chemical Physics, 1975, 63(9): 3821-3827.
[173] NOZIK A J, MEMMING R. Physical chemistry of semiconductor-liquidinterfaces [J]. The Journal of Physical Chemistry, 1996, 100(31):13061-13078.
[174] SORESCU D C, LEE J, AL-SAIDI W A, et al. CO2 adsorption on TiO2(110)rutile: Insight from dispersion-corrected density functional theorycalculations and scanning tunneling microscopy experiments [J]. The Journalof Chemical Physics, 2011, 134(10): 104707.
[175] TAMAKI Y, FURUBE A, MURAI M, et al. Dynamics of efficientelectron-hole separation in TiO2 nanoparticles revealed by femtosecondtransient absorption spectroscopy under the weak-excitation condition [J].Physical Chemistry Chemical Physics, 2007, 9(12): 1453-1460.
[176] RETICCIOLI M, SOKOLOVIĆ I, SCHMID M, et al. Interplay betweenadsorbates and polarons: CO on rutile TiO2(110) [J]. Physical Review Letters,2019, 122(1): 016805.
[177] MORGAN B J, WATSON G W. A DFT+ U description of oxygen vacancies atthe TiO2 rutile (110) surface [J]. Surface Science, 2007, 601(21): 5034-5041.
[178] MORGAN B J, WATSON G W. A density functional theory+U study ofoxygen vacancy formation at the (110),(100),(101), and (001) surfaces ofrutile TiO2 [J]. The Journal of Physical Chemistry C, 2009, 113(17):7322-7328.
[179] MAZHEIKA A, WANG Y-G, VALERO R, et al. Artificial-intelligence-drivendiscovery of catalyst genes with application to CO2 activation onsemiconductor oxides [J]. Nature Communications, 2022, 13(1): 1-13.
[180] HE H, ZAPOL P, CURTISS L A. Computational screening of dopants forphotocatalytic two-electron reduction of CO2 on anatase (101) surfaces [J].Energy & Environmental Science, 2012, 5(3): 6196-6205.
[181] MATHEW K, KOLLURU V C, MULA S, et al. Implicit self-consistent electrolyte model in plane-wave density-functional theory [J]. The Journal ofChemical Physics, 2019, 151(23): 234101.
[182] MATHEW K, SUNDARARAMAN R, LETCHWORTH-WEAVER K, et al.Implicit solvation model for density-functional study of nanocrystal surfacesand reaction pathways [J]. The Journal of Chemical Physics, 2014, 140(8):084106.
[183] GRIMME S, ANTONY J, EHRLICH S, et al. A consistent and accurate abinitio parametrization of density functional dispersion correction (DFT-D) forthe 94 elements H-Pu [J]. The Journal of Chemical Physics, 2010, 132(15):154104.
[184] CHEN G, WATERHOUSE G I, SHI R, et al. From Solar Energy to Fuels:Recent Advances in Light-Driven C1 Chemistry [J]. Angewandte ChemieInternational Edition, 2019, 58(49): 17528-17551.
[185] ZHAO Y, GAO W, LI S, et al. Solar-versus thermal-driven catalysis forenergy conversion [J]. Joule, 2019, 3(4): 920-37.
[186] FREUND H J, MEIJER G, SCHEFFLER M, et al. CO oxidation as aprototypical reaction for heterogeneous processes [J]. Angewandte ChemieInternational Edition, 2011, 50(43): 10064-10094.
[187] SAAVEDRA J, DOAN H A, PURSELL C J, et al. The critical role of water atthe gold-titania interface in catalytic CO oxidation [J]. Science, 2014,345(6204): 1599-1602.
[188] GREEN I X, TANG W, NEUROCK M, et al. Spectroscopic observation ofdual catalytic sites during oxidation of CO on a Au/TiO2 catalyst [J]. Science,2011, 333(6043): 736-739.
[189] CHEN M S, GOODMAN D W. The Structure of Catalytically Active Gold onTitania [J]. Science, 2004, 306(5694): 252-255.
[190] YANG F, GRACIANI J, EVANS J, et al. CO oxidation on inverseCeO(x)/Cu(111) catalysts: high catalytic activity and ceria-promoteddissociation of O2 [J]. Journal of the American Chemical Society, 2011,133(10): 3444-3451.
[191] KUSADA K, KOBAYASHI H, IKEDA R, et al. Solid Solution AlloyNanoparticles of Immiscible Pd and Ru Elements Neighboring on Rh:Changeover of the Thermodynamic Behavior for Hydrogen Storage andEnhanced CO-Oxidizing Ability [J]. Journal of the American ChemicalSociety, 2014 , 136(5): 1864-1871.
[192] SHIRLEY H, SU X, SANJANWALA H, et al. Durable Solar PoweredSystems with Ni-Catalysts for Conversion of CO2 or CO to CH4 [J]. Journal of the American Chemical Society, 2019, 141(16): 6617-6622.
[193] YAN-YAN, YU, XUE-QING, et al. CO Oxidation at Rutile TiO2(110): Roleof Oxygen Vacancies and Titanium Interstitials [J]. ACS Catalysis, 2015, 5(4):2042-2050.
[194] YING Z, DORONKIN D E, ZHAO Z, et al. Photothermal Catalysis overNon-plasmonic Pt/TiO2 Studied by Operando HERFD-XANES, ResonantXES and DRIFTS [J]. ACS Catalysis, 2018, 8(12): 11398-11406.
[195] WU X, LANG J, SUN Z, et al. Photocatalytic conversion of carbon monoxide:from pollutant removal to fuel production [J]. Applied Catalysis B:Environmental, 2021, 295: 120312.
[196] KOLOBOV N S, SVINTSITSKIY D, KOZLOVA E A, et al. UV-LEDphotocatalytic oxidation of carbon monoxide over TiO2 supported with noblemetal nanoparticles [J]. Chemical Engineering Journal, 2017, 314: 600-611.
[197] KAO F J, BUSCH D G, GOMES D, et al. Femtosecond versus nanosecondsurface photochemistry: O2+CO on Pt(111) at 80 K [J]. Physical ReviewLetters, 1993, 70(26): 4098-4101.
[198] LINSEBIGLER, AMY, RUSU, et al. Absence of platinum enhancement of aphotoreaction on TiO2-CO photooxidation on Pt/TiO2(110) [J]. Journal of theAmerican Chemical Society, 1996, 118(22): 5284-5289.
[199] JIAO Y, JIANG H, FENG C. RuO2/TiO2/Pt Ternary Photocatalysts withEpitaxial Heterojunction and Their Application in CO Oxidation [J]. ACSCatalysis, 2014, 4(7): 2249–2257.
[200] YOON Y, WANG Y G, ROUSSEAU R, et al. Impact of Nonadiabatic ChargeTransfer on the Rate of Redox Chemistry of Carbon Oxides on RutileTiO2(110) Surface [J]. ACS Catalysis, 2015, 5(3): 1764-1771.
[201] KOLOBOV N S, SELISHCHEV D S, BUKHTIYAROV A V, et al. UV-LEDPhotocatalytic Oxidation of CO over the Pd/TiO2 Catalysts Synthesized bythe Decomposition of Pd(acac)2 [J]. Materials Today: Proceedings, 2017,4(11): 11356-11359.
[202] HENDERSON M A. A Surface Science Perspective on TiO2 Photocatalysis[J]. Surface Science Reports, 2011, 66(6-7): 185-297.
[203] LU G, LINSEBIGLER A, YATES JR J T. The photochemical identification oftwo chemisorption states for molecular oxygen on TiO2(110) [J]. The Journalof Chemical Physics, 1995, 102(7): 3005-3008.
[204] HENDERSON M A, EPLING W S, PERKINS C L, et al. Interaction ofmolecular oxygen with the vacuum-annealed TiO2(110) surface: molecularand dissociative channels [J]. The Journal of Physical Chemistry B, 1999, 103(25): 5328-5337.
[205] SCHEIBER P, RISS A, SCHMID M, et al. Observation and destruction of anelusive adsorbate with STM: O2/TiO2(110) [J]. Physical Review Letters, 2010,105(21): 216101.
[206] WANG D, HAN D, LI X-B, et al. Determination of formation and ionizationenergies of charged defects in two-dimensional materials [J]. Physical ReviewLetters, 2015, 114(19): 196801.
[207] XIAO J, YANG K, GUO D, et al. Realistic dimension-independent approachfor charged-defect calculations in semiconductors [J]. Physical Review B,2020, 101(16): 165306.
[208] WANG D, WANG H, HU P. Identifying the distinct features of geometricstructures for hole trapping to generate radicals on rutile TiO2(110) inphotooxidation using density functional theory calculations with hybridfunctional [J]. Physical Chemistry Chemical Physics, 2015, 17(3):1549-1555.
[209] THOMPSON T L, YATES J T. Surface science studies of the photoactivationof TiO2 new photochemical processes [J]. Chemical Reviews, 2006, 106(10):4428-4453.
[210] THOMPSON T L, YATES J T. TiO2-based photocatalysis: surface defects,oxygen and charge transfer [J]. Topics in Catalysis, 2005, 35(3): 197-210.
[211] PERKINS C L, HENDERSON M A. Photodesorption and Trapping ofMolecular Oxygen at the TiO2(110)-Water Ice Interface [J]. The Journal ofPhysical Chemistry B, 2001, 105(18): 3856-3863.
[212] THOMPSON T L, YATES J T. Control of a surface photochemical process byfractal electron transport across the surface: O2 photodesorption fromTiO2(110) [J]. The Journal of Physical Chemistry B, 2006, 110(14):7431-7435.
[213] SPORLEDER D, WILSON D P, WHITE M G. Final state distributions of O2photodesorbed from TiO2(110) [J]. The Journal of Physical Chemistry C,2009, 113(30): 13180-13191.
[214] DE LARA-CASTELLS M, KRAUSE J L. Theoretical study of theUV-induced desorption of molecular oxygen from the reduced TiO2(110)surface [J]. The Journal of Chemical Physics, 2003, 118(11): 5098-5105.
[215] LIDE D R. CRC handbook of chemistry and physics [M]. CRC press, 2004.
[216] ASAHI R, MORIKAWA T, IRIE H, et al. Nitrogen-doped titanium dioxide asvisible-light-sensitive photocatalyst: designs, developments, and prospects [J].Chemical Reviews, 2014, 114(19): 9824-9852.
[217] SATO S. Photocatalytic activity of NOx-doped TiO2 in the visible light region[J]. Chemical Physics Letters, 1986, 123(1-2): 126-128.
[218] DI VALENTIN C, PACCHIONI G, SELLONI A. Origin of the differentphotoactivity of N-doped anatase and rutile TiO2 [J]. Physical Review B,2004, 70(8): 085116.
[219] LIVRAGHI S, PAGANINI M C, GIAMELLO E, et al. Origin of photoactivityof nitrogen-doped titanium dioxide under visible light [J]. Journal of theAmerican Chemical Society, 2006, 128(49): 15666-71.
[220] BATZILL M, MORALES E H, DIEBOLD U. Influence of nitrogen doping onthe defect formation and surface properties of TiO2 rutile and anatase [J].Physical Review Letters, 2006, 96(2): 026103.
[221] YU Y, YANG X, ZHAO Y, et al. Engineering the band gap states of the rutileTiO2(110) surface by modulating the active heteroatom [J]. AngewandteChemie International Edition, 2018, 57(28): 8550-8554.
[222] ZUNGER A. Practical doping principles [J]. Applied Physics Letters, 2003,83(1): 57-59.
[223] WEI S-H. Overcoming the doping bottleneck in semiconductors [J].Computational Materials Science, 2004, 30(3-4): 337-348.
[224] ZUNGER A, MALYI O I. Understanding doping of quantum materials [J].Chemical Reviews, 2021, 121(5): 3031-3060.
[225] CAI X, SABINO F P, JANOTTI A, et al. Approach to achieving a p-typetransparent conducting oxide: Doping of bismuth-alloyed Ga2O3 with astrongly correlated band edge state [J]. Physical Review B, 2021, 103(11):115205.
[226] SOKOLOVIĆ I, RETICCIOLI M, ČALKOVSKý M, et al. Resolving theadsorption of molecular O2 on the rutile TiO2(110) surface by noncontactatomic force microscopy [J]. Proceedings of the National Academy ofSciences, 2020, 117(26): 14827-14837.
[227] TILOCCA A, SELLONI A. O2 and vacancy diffusion on rutile (110):pathways and electronic properties [J]. ChemPhysChem, 2005, 6(9):1911-1916.