Role of the Surface Lewis Acid and Base Sites in the Adsorption of CO2 on Titania Nanotubes and Platinized Titania Nanotubes: An in Situ FT-IR Study

View Author Information
Institute for Catalysis in Energy Processes, Department of Chemistry, §Department of Civil and Environmental Engineering, Northwestern University, Evanston, Illinois 60208, United States
Cite this: J. Phys. Chem. C 2013, 117, 24, 12661–12678
Publication Date (Web):June 7, 2013
Copyright © 2013 American Chemical Society
Article Views
Read OnlinePDF (2 MB)
Supporting Info (1)»


An understanding of the adsorption of CO2, the first step in its photoreduction, is necessary for a full understanding of the photoreduction process. As such, the reactive adsorption of CO2 on oxidized, reduced, and platinized TiO2 nanotubes (Ti-NTs) was studied using infrared spectroscopy. The Ti-NTs were characterized with TEM and XRD, and XPS was used to determine the oxidation state as a function of oxidation, reduction, and platinization. The XPS data demonstrate that upon oxidation, surface O atoms become more electronegative, producing sites that can be characterized as strong Lewis bases, and the corresponding Ti becomes more electropositive producing sites that can be characterized as strong Lewis acids. Reduction of the Ti-NTs produces Ti3+ species, a very weak Lewis acid, along with a splitting of the Ti4+ peak, representing two sites, which correlate with O sites with a corresponding change in oxidation state. Ti3+ is not observed on reduction of the platinized Ti-NTs, presumably because Pt acts as an electron sink. Exposure of the treated Ti-NTs to CO2 leads to the formation of differing amounts of bidentate and monodentate carbonates, as well as bicarbonates, where the preference for formation of a given species is rationalized in terms of surface Lewis acidity and or Lewis basicity and the availability of hydrogen. Our data suggest that one source of hydrogen is water that remains adsorbed to the Ti-NTs even after heating to 350 °C and that reduced platinized NTs can activate H2. Carboxylates, which involve CO2 moieties and are similar to what would be expected for adsorbed CO2, a postulated intermediate in CO2 photoreduction, are also observed but only on the reduced Ti-NTs, which is the only surface on which Ti3+/O vacancy formation is observed.

Supporting Information

Jump To

Results of the TPR experiments, along with some EDAX, TEM data, and Scheme S6. This material is available free of charge via the Internet at

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 68 publications.

  1. Kaustava Bhattacharyya, Gurudas P. Mane, Vinayak Rane, Arvind K. Tripathi, Avesh K. Tyagi. Selective CO2 Photoreduction with Cu-Doped TiO2 Photocatalyst: Delineating the Crucial Role of Cu-Oxidation State and Oxygen Vacancies. The Journal of Physical Chemistry C 2021, 125 (3) , 1793-1810.
  2. Yuan-Peng Du, Ali M. Bahmanpour, Luka Milošević, Florent Héroguel, Mounir D. Mensi, Oliver Kröcher, Jeremy S. Luterbacher. Engineering the ZrO2–Pd Interface for Selective CO2 Hydrogenation by Overcoating an Atomically Dispersed Pd Precatalyst. ACS Catalysis 2020, 10 (20) , 12058-12070.
  3. Sumika Yoshizawa, Zeai Huang, Kentaro Teramura, Hiroyuki Asakura, Saburo Hosokawa, Tsunehiro Tanaka. Important Role of Strontium Atom on the Surface of Sr2KTa5O15 with a Tetragonal Tungsten Bronze Structure to Improve Adsorption of CO2 for Photocatalytic Conversion of CO2 by H2O. ACS Applied Materials & Interfaces 2019, 11 (41) , 37875-37884.
  4. Eri Uematsu, Atsushi Itadani, Hideki Hashimoto, Kazuyoshi Uematsu, Kenji Toda, Mineo Sato. Tubular Titanates: Alkali-Metal Ion-Exchange Features and Carbon Dioxide Adsorption at Room Temperature. Industrial & Engineering Chemistry Research 2019, 58 (13) , 5168-5174.
  5. Ilango Aswin Kumar, Natrayasamy Viswanathan. Hydrothermal Fabrication of Zirconium Oxyhydroxide Capped Chitosan/Kaolin Framework for Highly Selective Nitrate and Phosphate Retention. Industrial & Engineering Chemistry Research 2018, 57 (43) , 14470-14481.
  6. Néstor E. Mendieta-Reyes, Ana Korina Díaz-García, and Roberto Gómez . Simultaneous Electrocatalytic CO2 Reduction and Enhanced Electrochromic Effect at WO3 Nanostructured Electrodes in Acetonitrile. ACS Catalysis 2018, 8 (3) , 1903-1912.
  7. Anmin Zheng, Shang-Bin Liu, and Feng Deng . 31P NMR Chemical Shifts of Phosphorus Probes as Reliable and Practical Acidity Scales for Solid and Liquid Catalysts. Chemical Reviews 2017, 117 (19) , 12475-12531.
  8. Kulbir Kaur Ghuman, Laura B. Hoch, Thomas E. Wood, Charles Mims, Chandra Veer Singh, and Geoffrey A. Ozin . Surface Analogues of Molecular Frustrated Lewis Pairs in Heterogeneous CO2 Hydrogenation Catalysis. ACS Catalysis 2016, 6 (9) , 5764-5770.
  9. Ganganahalli K. Ramesha, Joan F. Brennecke, and Prashant V. Kamat . Origin of Catalytic Effect in the Reduction of CO2 at Nanostructured TiO2 Films. ACS Catalysis 2014, 4 (9) , 3249-3254.
  10. Zhiqiao He, Lina Wen, Da Wang, Yijun Xue, Qianwen Lu, Cuiwei Wu, Jianmeng Chen, and Shuang Song . Photocatalytic Reduction of CO2 in Aqueous Solution on Surface-Fluorinated Anatase TiO2 Nanosheets with Exposed {001} Facets. Energy & Fuels 2014, 28 (6) , 3982-3993.
  11. Roman G. Pavelko, Joong-Ki Choi, Atsushi Urakawa, Masayoshi Yuasa, Tetsuya Kida, and Kengo Shimanoe . H2O/D2O Exchange on SnO2 Materials in the Presence of CO: Operando Spectroscopic and Electric Resistance Measurements. The Journal of Physical Chemistry C 2014, 118 (5) , 2554-2563.
  12. Weiqiang Wu, Kaustava Bhattacharyya, Kimberly Gray, and Eric Weitz . Photoinduced Reactions of Surface-Bound Species on Titania Nanotubes and Platinized Titania Nanotubes: An in Situ FTIR Study. The Journal of Physical Chemistry C 2013, 117 (40) , 20643-20655.
  13. Vivek Srivastava. CO2 Hydrogenation over Ru-NPs Supported Amine-Functionalized SBA-15 Catalyst: Structure–Reactivity Relationship Study. Catalysis Letters 2021, 151 (12) , 3704-3720.
  14. Alejandra Chavez‐Mulsa, Juan C. Fierro‐Gonzalez, Brent E. Handy, Iván Alonso Santos‐López, Sergio Aarón Jimenez‐Lam, David A. De Haro Del Río, Javier Rivera De la Rosa, Gerardo Antonio Flores‐Escamilla. Ethylene Hydroformylation with Carbon Dioxide Catalyzed by Ruthenium Supported on Titanate Nanotubes: Infrared Spectroscopic Evidence of Surface Species. ChemistrySelect 2021, 6 (40) , 10758-10766.
  15. Shaojie Wei, Qianqian Heng, Yufeng Wu, Wei Chen, Xiying Li, Wenfeng Shangguan. Improved photocatalytic CO2 conversion efficiency on Ag loaded porous Ta2O5. Applied Surface Science 2021, 563 , 150273.
  16. Shibu Joseph, Albin John P. Paul Winston, S. Muthupandi, P. Shobha, S. Mary Margaret, P. Sagayaraj, . Performance of Natural Dye Extracted from Annatto, Black Plum, Turmeric, Red Spinach, and Cactus as Photosensitizers in TiO2NP/TiNT Composites for Solar Cell Applications. Journal of Nanomaterials 2021, 2021 , 1-12.
  17. Bowen Liu, Peng Bai, Yang Wang, Zhun Dong, Pingping Wu, Svetlana Mintova, Zifeng Yan. Highly stable Ni/ ZnO‐Al 2 O 3 adsorbent promoted by TiO 2 for reactive adsorption desulfurization. EcoMat 2021, 3 (4)
  18. Xule Pei, Tong Zhang, Jingyi Zhong, Zaihao Chen, Chuanjia Jiang, Wei Chen. Substoichiometric titanium oxide Ti2O3 exhibits greater efficiency in enhancing hydrolysis of 1,1,2,2-tetrachloroethane than TiO2 nanomaterials. Science of The Total Environment 2021, 774 , 145705.
  19. Yufeng Li, Bing Liu, Jie Liu, Ting Wang, Yu Shen, Ke Zheng, Feng Jiang, Yuebing Xu, Xiaohao Liu. Tuning the Lewis acidity of ZrO 2 for efficient conversion of CH 4 and CO 2 into acetic acid. New Journal of Chemistry 2021, 45 (20) , 8978-8985.
  20. Kun Jiang, Jin Zhang, Rui Luo, Yingfei Wan, Zengjian Liu, Jinwei Chen. A facile synthesis of Zn-doped TiO 2 nanoparticles with highly exposed (001) facets for enhanced photocatalytic performance. RSC Advances 2021, 11 (13) , 7627-7632.
  21. Kallyni Irikura, João Angelo Lima Perini, Jader Barbosa Silva Flor, Regina Célia Galvão Frem, Maria Valnice Boldrin Zanoni. Direct synthesis of Ru3(BTC)2 metal-organic framework on a Ti/TiO2NT platform for improved performance in the photoelectroreduction of CO2. Journal of CO2 Utilization 2021, 43 , 101364.
  22. Beatriz Costa e Silva, Kallyni Irikura, Jader Barbosa Silva Flor, Rodrigo Morais Menezes dos Santos, Abdessadek Lachgar, Regina Célia Galvão Frem, Maria Valnice Boldrin Zanoni. Electrochemical preparation of Cu/Cu2O-Cu(BDC) metal-organic framework electrodes for photoelectrocatalytic reduction of CO2. Journal of CO2 Utilization 2020, 42 , 101299.
  23. Ying Wang, Xiaotong Shang, Jinni Shen, Zizhong Zhang, Debao Wang, Jinjin Lin, Jeffrey C. S. Wu, Xianzhi Fu, Xuxu Wang, Can Li. Direct and indirect Z-scheme heterostructure-coupled photosystem enabling cooperation of CO2 reduction and H2O oxidation. Nature Communications 2020, 11 (1)
  24. Fan Fang, Peng Zhao, Nengjie Feng, Hui Wan, Guofeng Guan. Surface engineering on porous perovskite-type La0.6Sr0.4CoO3-δ nanotubes for an enhanced performance in diesel soot elimination. Journal of Hazardous Materials 2020, 399 , 123014.
  25. Eri Uematsu, Atsushi Itadani, Kazuyoshi Uematsu, Kenji Toda, Mineo Sato. IR study on adsorption of carbon dioxide on alkaline earth metal ion-exchanged titanate nanotubes at room temperature. Vibrational Spectroscopy 2020, 109 , 103088.
  26. Sheng Zeng, Ehsan Vahidzadeh, Collin G. VanEssen, Piyush Kar, Ryan Kisslinger, Ankur Goswami, Yun Zhang, Najia Mahdi, Saralyn Riddell, Alexander E. Kobryn, Sergey Gusarov, Pawan Kumar, Karthik Shankar. Optical control of selectivity of high rate CO2 photoreduction via interband- or hot electron Z-scheme reaction pathways in Au-TiO2 plasmonic photonic crystal photocatalyst. Applied Catalysis B: Environmental 2020, 267 , 118644.
  27. Minsung Kim, Sang Hoon Kim, Jung-Hyun Lee, Jongsik Kim. Unravelling lewis acidic and reductive characters of normal and inverse nickel-cobalt thiospinels in directing catalytic H2O2 cleavage. Journal of Hazardous Materials 2020, 392 , 122347.
  28. M. A. A. Aziz, A. A. Jalil, S. Wongsakulphasatch, Dai-Viet N. Vo. Understanding the role of surface basic sites of catalysts in CO 2 activation in dry reforming of methane: a short review. Catalysis Science & Technology 2020, 10 (1) , 35-45.
  29. Rupak Roy, Srimanta Ray. Effect of various pretreatments on energy recovery from waste biomass. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects 2019, , 1-13.
  30. Chang-Min Cho, Naoyoshi Nunotani, Nobuhito Imanaka. Effect of oxygen vacancies on direct N 2 O decomposition over ZrO 2 -Y 2 O 3 catalysts. Journal of Asian Ceramic Societies 2019, 7 (4) , 518-523.
  31. Chao Liu, Scott L. Nauert, Marco A. Alsina, Dingdi Wang, Alexander Grant, Kai He, Eric Weitz, Michael Nolan, Kimberly A. Gray, Justin M. Notestein. Role of surface reconstruction on Cu/TiO2 nanotubes for CO2 conversion. Applied Catalysis B: Environmental 2019, 255 , 117754.
  32. Bingbing Hu, Maocong Hu, Qiang Guo, Kang Wang, Xitao Wang. In-vacancy engineered plate-like In(OH)3 for effective photocatalytic reduction of CO2 with H2O vapor. Applied Catalysis B: Environmental 2019, 253 , 77-87.
  33. Yawen Wang, Da He, Hongyu Chen, Dunwei Wang. Catalysts in electro-, photo- and photoelectrocatalytic CO2 reduction reactions. Journal of Photochemistry and Photobiology C: Photochemistry Reviews 2019, 40 , 117-149.
  34. Bing Bai, Qingsong Chen, Xiuhui Zhao, Dehuang Zhuo, Zhongning Xu, Zhiqiao Wang, Mingyan Wu, Hongzi Tan, Siyan Peng, Guocong Guo. Enhancing Electroreduction of CO 2 to Formate of Pd Catalysts Loaded on TiO 2 Nanotubes Arrays by N, B‐Support Modification. ChemistrySelect 2019, 4 (29) , 8626-8633.
  35. Jesús Roberto Ruiz‐García, Juan Carlos Fierro‐Gonzalez, Brent E. Handy, Laura Hinojosa‐Reyes, David A. De Haro Del Río, Carlos J. Lucio‐Ortiz, Sergio Valle‐Cervantes, Gerardo A. Flores‐Escamilla. An In Situ Infrared Study of CO 2 Hydrogenation to Formic Acid by Using Rhodium Supported on Titanate Nanotubes as Catalysts. ChemistrySelect 2019, 4 (14) , 4206-4216.
  36. Gelson T.S.T. da Silva, André E. Nogueira, Jéssica A. Oliveira, Juliana A. Torres, Osmando F. Lopes, Caue Ribeiro. Acidic surface niobium pentoxide is catalytic active for CO2 photoreduction. Applied Catalysis B: Environmental 2019, 242 , 349-357.
  37. SK Hossain, Junaid Saleem, SleemUr Rahman, Syed Zaidi, Gordon McKay, Chin Cheng. Synthesis and Evaluation of Copper-Supported Titanium Oxide Nanotubes as Electrocatalyst for the Electrochemical Reduction of Carbon Oxide to Organics. Catalysts 2019, 9 (3) , 298.
  38. Qian Chen, Xianjie Chen, Minling Fang, Jiayu Chen, Yongjian Li, Zhaoxiong Xie, Qin Kuang, Lansun Zheng. Photo-induced Au–Pd alloying at TiO 2 {101} facets enables robust CO 2 photocatalytic reduction into hydrocarbon fuels. Journal of Materials Chemistry A 2019, 7 (3) , 1334-1340.
  39. Chandra Sekhar Kuppan, Murthy Chavali. CO2 Sequestration: Processes and Methodologies. 2019,,, 1-50.
  40. Chandra Sekhar Kuppan, Murthy Chavali. CO2 Sequestration: Processes and Methodologies. 2019,,, 619-668.
  41. Zhaoyu Ma, Penghui Li, Liqun Ye, Li Wang, Haiquan Xie, Ying Zhou. Selectivity reversal of photocatalytic CO 2 reduction by Pt loading. Catalysis Science & Technology 2018, 8 (20) , 5129-5132.
  42. Mark Isaacs, Brunella Barbero, Lee Durndell, Anthony Hilton, Luca Olivi, Christopher Parlett, Karen Wilson, Adam Lee. Tunable Silver-Functionalized Porous Frameworks for Antibacterial Applications. Antibiotics 2018, 7 (3) , 55.
  43. Rui Ma, Yunpeng Li, Guandong Wu, Yufei He, Junting Feng, Yingying Zhao, Dianqing Li. Fabrication of Pd-based metal-acid-alkali multifunctional catalysts for one-pot synthesis of MIBK. Chinese Journal of Catalysis 2018, 39 (8) , 1384-1394.
  44. J.C. Cardoso, S. Stulp, J.F. de Brito, J.B.S. Flor, R.C.G. Frem, M.V.B. Zanoni. MOFs based on ZIF-8 deposited on TiO2 nanotubes increase the surface adsorption of CO2 and its photoelectrocatalytic reduction to alcohols in aqueous media. Applied Catalysis B: Environmental 2018, 225 , 563-573.
  45. Yabo Wang, Jie Zhao, Yingxuan Li, Chuanyi Wang. Selective photocatalytic CO2 reduction to CH4 over Pt/In2O3: Significant role of hydrogen adatom. Applied Catalysis B: Environmental 2018, 226 , 544-553.
  46. Ruslan V. Mikhaylov, Konstantin V. Nikitin, Nadezhda I. Glazkova, Vyacheslav N. Kuznetsov. Temperature-programmed desorption of CO2, formed by CO photooxidation on TiO2 surface. Journal of Photochemistry and Photobiology A: Chemistry 2018, 360 , 255-261.
  47. João A. Lima Perini, Juliano C. Cardoso, Juliana F. de Brito, Maria V. Boldrin Zanoni. Contribution of thin films of ZrO2 on TiO2 nanotubes electrodes applied in the photoelectrocatalytic CO2 conversion. Journal of CO2 Utilization 2018, 25 , 254-263.
  48. Xianmei Xiang, Fuping Pan, Ying Li. A review on adsorption-enhanced photoreduction of carbon dioxide by nanocomposite materials. Advanced Composites and Hybrid Materials 2018, 1 (1) , 6-31.
  49. Juliana Ferreira de Brito, Felipe Fantinato Hudari, Maria Valnice Boldrin Zanoni. Photoelectrocatalytic performance of nanostructured p-n junction NtTiO2/NsCuO electrode in the selective conversion of CO2 to methanol at low bias potentials. Journal of CO2 Utilization 2018, 24 , 81-88.
  50. Faris A. J. Al-Doghachi, Yun Hin Taufiq-Yap. CO 2 Reforming of Methane over Ni/MgO Catalysts Promoted with Zr and La Oxides. ChemistrySelect 2018, 3 (2) , 816-827.
  51. Dr. Chandrasekhar Kuppan, Chavali Yadav. CO2 Sequestration: Processes and Methodologies. 2018,,, 1-50.
  52. Yanlong Yu, Zijian Lan, Limei Guo, Enjun Wang, Jianghong Yao, Yaan Cao. Synergistic effects of Zn and Pd species in TiO 2 towards efficient photo-reduction of CO 2 into CH 4. New Journal of Chemistry 2018, 42 (1) , 483-488.
  53. Ramya G. Nair, S. Mazumdar, B. Modak, R. Bapat, P. Ayyub, Kaustava Bhattacharyya. The role of surface O-vacancies in the photocatalytic oxidation of Methylene Blue by Zn-doped TiO 2 : A Mechanistic approach. Journal of Photochemistry and Photobiology A: Chemistry 2017, 345 , 36-53.
  54. Shibu Joseph, S. Jacob Melvin Boby, D. Muthu Gnana Theresa Nathan, P. Sagayaraj. Investigation on the role of cost effective cathode materials for fabrication of efficient DSSCs with TiNT/TiO 2 nanocomposite photoanodes. Solar Energy Materials and Solar Cells 2017, 165 , 72-81.
  55. K.C. Schwartzenberg, J.W.J. Hamilton, A.K. Lucid, E. Weitz, J. Notestein, M. Nolan, J.A. Byrne, K.A. Gray. Multifunctional photo/thermal catalysts for the reduction of carbon dioxide. Catalysis Today 2017, 280 , 65-73.
  56. Jiajia Guo, Kang Wang, Xitao Wang. Photocatalytic reduction of CO 2 with H 2 O vapor under visible light over Ce doped ZnFe 2 O 4. Catalysis Science & Technology 2017, 7 (24) , 6013-6025.
  57. Stefano Sterchele, Marco Bortolus, Pierdomenico Biasi, Dan Boström, Jyri-Pekka Mikkola, Tapio Salmi. Is selective hydrogenation of molecular oxygen to H2O2 affected by strong metal–support interactions on Pd/TiO2 catalysts? A case study using commercially available TiO2. Comptes Rendus Chimie 2016, 19 (8) , 1011-1020.
  58. Munhee Lee, Yongbeom Seo, Hye Sun Shin, Changbum Jo, Ryong Ryoo. Anatase TiO2 nanosheets with surface acid sites for Friedel–Crafts alkylation. Microporous and Mesoporous Materials 2016, 222 , 185-191.
  59. Zhiqiao He, Juntao Tang, Jie Shen, Jianmeng Chen, Shuang Song. Enhancement of photocatalytic reduction of CO2 to CH4 over TiO2 nanosheets by modifying with sulfuric acid. Applied Surface Science 2016, 364 , 416-427.
  60. Anna Pougin, Martin Dilla, Jennifer Strunk. Identification and exclusion of intermediates of photocatalytic CO 2 reduction on TiO 2 under conditions of highest purity. Physical Chemistry Chemical Physics 2016, 18 (16) , 10809-10817.
  61. P. Tamilarasan, S. Ramaprabhu. Amine-rich ionic liquid grafted graphene for sub-ambient carbon dioxide adsorption. RSC Advances 2016, 6 (4) , 3032-3040.
  62. Zhiqiao He, Yan Yu, Da Wang, Juntao Tang, Jianmeng Chen, Shuang Song. Photocatalytic reduction of carbon dioxide using iodine-doped titanium dioxide with high exposed {001} facets under visible light. RSC Advances 2016, 6 (28) , 23134-23140.
  63. Kaustava Bhattacharyya, Weiqiang Wu, Eric Weitz, Baiju Vijayan, Kimberly Gray. Probing Water and CO2 Interactions at the Surface of Collapsed Titania Nanotubes Using IR Spectroscopy. Molecules 2015, 20 (9) , 15469-15487.
  64. Zhenxin Xu, Ning Wang, Wei Chu, Jie Deng, Shizhong Luo. In situ controllable assembly of layered-double-hydroxide-based nickel nanocatalysts for carbon dioxide reforming of methane. Catalysis Science & Technology 2015, 5 (3) , 1588-1597.
  65. Mohamed Mokhtar Mohamed. Gold loaded titanium dioxide–carbon nanotube composites as active photocatalysts for cyclohexane oxidation at ambient conditions. RSC Advances 2015, 5 (57) , 46405-46414.
  66. X. Du, L. J. France, V. L. Kuznetsov, T. Xiao, P. P. Edwards, Hamid AlMegren, Abdulaziz Bagabas. Dry reforming of methane over ZrO2-supported Co–Mo carbide catalyst. Applied Petrochemical Research 2014, 4 (1) , 137-144.
  67. Lianjun Liu, Cunyu Zhao, Daniel Pitts, Huilei Zhao, Ying Li. CO 2 photoreduction with H 2 O vapor by porous MgO–TiO 2 microspheres: effects of surface MgO dispersion and CO 2 adsorption–desorption dynamics. Catal. Sci. Technol. 2014, 4 (6) , 1539-1546.
  68. Hipassia M. Moura, Heloise O. Pastore. Functionalized mesoporous solids based on magadiite and [Al]-magadiite. Dalton Transactions 2014, 43 (27) , 10471.