Nanocomposite of N-Doped TiO2 Nanorods and Graphene as an Effective Electrocatalyst for the Oxygen Reduction Reaction

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School of Chemistry and Chemical Engineering, Anhui University, Hefei, Anhui 230601, P. R. China
Department of Chemical and Materials Engineering, University of Kentucky, Lexington, Kentucky 40506, United States
*E-mail: [email protected]. Fax: +86-0551-63861475.
*E-mail: [email protected]. Fax: +86-0551-63861475.
Cite this: ACS Appl. Mater. Interfaces 2014, 6, 24, 21978–21985
Publication Date (Web):November 18, 2014
Copyright © 2014 American Chemical Society
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Developing an effective electrocatalyst for the oxygen reduction reaction is a momentous issue in fuel cells. In this paper, we successfully synthesized the N-doped TiO2 nanorods/graphene (N-TiO2/NG) nanocomposite, which comprise the N-doped TiO2 (N-TiO2) nanorods (40–60 nm diameter and 90–300 nm length) and self-assembled nitrogen-doped graphene (NG) networks. We found that the nanocomposite exhibits great oxygen reduction reaction (ORR) electrocatalytic performance and also shows long durability and methanol tolerance than that of the commercial 20% Pt/C catalyst. This new nanocomposite may also have potential applications in other fields, which are related to energy storage, gas sensors, photocatalysis, and so on.

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EDX results of N-TiO2/NG-0.4. SEM images of NG, N-TiO2/NG-0.2, and N-TiO2/NG-0.6. XPS survey of the N-TiO2/NG-0.4. ORR polarization curves for NG, N-TiO2/NG-0.2, N-TiO2/NG-0.6, and commercial Pt/C catalysts recorded in an O2-saturated 0.1 M KOH at the different rotation rate. K-L plots for NG, N-TiO2/NG-0.2, N-TiO2/NG-0.6, and commercial Pt/C at different potentials. RRDE test of the ORR on NG, N-TiO2/NG-0.2, and N-TiO2/NG-0.6 in an O2-saturated 0.1 M KOH (1600 rpm). This material is available free of charge via the Internet at

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  2. Eungjun Lee, Changmin Park, Dong Wook Lee, Gibaek Lee, Hee-Young Park, Jong Hyun Jang, Hyoung-Juhn Kim, Yung-Eun Sung, Yongsug Tak, Sung Jong Yoo. Tunable Synthesis of N,C-Codoped Ti3+-Enriched Titanium Oxide Support for Highly Durable PEMFC Cathode. ACS Catalysis 2020, 10 (20) , 12080-12090.
  3. Shi-Fang Duan, Yong-Fei Ji, Wei Wang, Dong-Fang Han, Hao-Yu Wang, Qiu-Yu Wei, Chun-Feng Li, Fei Jia, Dong-Xue Han, Li Niu, Dong-Dong Qin, Chun-Lan Tao. Unraveling the Impact of Electrochemically Created Oxygen Vacancies on the Performance of ZnO Nanowire Photoanodes. ACS Sustainable Chemistry & Engineering 2019, 7 (21) , 18165-18173.
  4. Likun Wang, Yuchen Zhou, Yuanxi Yang, Ashwanth Subramanian, Kim Kisslinger, Xianghao Zuo, Ya-Chen Chuang, Yifan Yin, Chang-Yong Nam, Miriam H. Rafailovich. Suppression of Carbon Monoxide Poisoning in Proton Exchange Membrane Fuel Cells via Gold Nanoparticle/Titania Ultrathin Film Heterogeneous Catalysts. ACS Applied Energy Materials 2019, 2 (5) , 3479-3487.
  5. Likun Wang, Yuchen Zhou, Janis Timoshenko, Shizhong Liu, Qiao Qiao, Kim Kisslinger, Michael Cuiffo, Ya-Chen Chuang, Xianghao Zuo, Yuan Xue, Yichen Guo, Cheng Pan, Hongfei Li, Chang-Yong Nam, Stoyan Bliznakov, Ping Liu, Anatoly I. Frenkel, Yimei Zhu, Miriam H. Rafailovich. Designing Nanoplatelet Alloy/Nafion Catalytic Interface for Optimization of PEMFCs: Performance, Durability, and CO Resistance. ACS Catalysis 2019, 9 (2) , 1446-1456.
  6. Gan Wang, Sanpei Zhang, Rong Qian, Zhaoyin Wen. Atomic-Thick TiO2(B) Nanosheets Decorated with Ultrafine Co3O4 Nanocrystals As a Highly Efficient Catalyst for Lithium–Oxygen Battery. ACS Applied Materials & Interfaces 2018, 10 (48) , 41398-41406.
  7. Andrea Folli, Jonathan Z. Bloh, Katherine Armstrong, Emma Richards, Damien M. Murphy, Li Lu, Christopher J. Kiely, David J. Morgan, Ronald I. Smith, Abbie C. Mclaughlin, Donald E. Macphee. Improving the Selectivity of Photocatalytic NOx Abatement through Improved O2 Reduction Pathways Using Ti0.909W0.091O2Nx Semiconductor Nanoparticles: From Characterization to Photocatalytic Performance. ACS Catalysis 2018, 8 (8) , 6927-6938.
  8. Jiajun Wang, Shyam Kattel, Zongyuan Wang, Jingguang G. Chen, Chang-Jun Liu. L-Phenylalanine-Templated Platinum Catalyst with Enhanced Performance for Oxygen Reduction Reaction. ACS Applied Materials & Interfaces 2018, 10 (25) , 21321-21327.
  9. Shangbin Jin, Cuiling Li, Lok Kumar Shrestha, Yusuke Yamauchi, Katsuhiko Ariga, and Jonathan P. Hill . Simple Fabrication of Titanium Dioxide/N-Doped Carbon Hybrid Material as Non-Precious Metal Electrocatalyst for the Oxygen Reduction Reaction. ACS Applied Materials & Interfaces 2017, 9 (22) , 18782-18789.
  10. Seul Lee, Da-Hee Kwak, Sang-Beom Han, Young-Woo Lee, Jin-Yeon Lee, In-Ae Choi, Hyun-Suk Park, Jin-Young Park, and Kyung-Won Park . Bimodal Porous Iron/Nitrogen-Doped Highly Crystalline Carbon Nanostructure as a Cathode Catalyst for the Oxygen Reduction Reaction in an Acid Medium. ACS Catalysis 2016, 6 (8) , 5095-5102.
  11. Wei-Tang Yao, Liang Yu, Peng-Fei Yao, Kang Wei, Su-Ling Han, Ping Chen, and Jin-Song Xie . Bulk Production of Nonprecious Metal Catalysts from Cheap Starch as Precursor and Their Excellent Electrochemical Activity. ACS Sustainable Chemistry & Engineering 2016, 4 (6) , 3235-3244.
  12. Peng Zhang, Xiuli Hou, Lei Liu, Jianli Mi, and Mingdong Dong . Two-Dimensional π-Conjugated Metal Bis(dithiolene) Complex Nanosheets as Selective Catalysts for Oxygen Reduction Reaction. The Journal of Physical Chemistry C 2015, 119 (50) , 28028-28037.
  13. Weiwei Gu, Jingjun Liu, Mingan Hu, Feng Wang, and Ye Song . La2O2CO3 Encapsulated La2O3 Nanoparticles Supported on Carbon as Superior Electrocatalysts for Oxygen Reduction Reaction. ACS Applied Materials & Interfaces 2015, 7 (48) , 26914-26922.
  14. Yongliang Liao, Yuan Gao, Shenmin Zhu, Junsheng Zheng, Zhixin Chen, Chao Yin, Xianghong Lou, and Di Zhang . Facile Fabrication of N-Doped Graphene as Efficient Electrocatalyst for Oxygen Reduction Reaction. ACS Applied Materials & Interfaces 2015, 7 (35) , 19619-19625.
  15. Qiang Liu, Marco Ranocchiari, Jeroen A. van Bokhoven. Catalyst overcoating engineering towards high-performance electrocatalysis. Chemical Society Reviews 2022, 528
  16. Zhipeng Ding, Mingxuan Sun, Wenzhu Liu, Wangbing Sun, Xianglong Meng, Yongqiang Zheng. Ultrasonically synthesized N-TiO2/Ti3C2 composites: Enhancing sonophotocatalytic activity for pollutant degradation and nitrogen fixation. Separation and Purification Technology 2021, 276 , 119287.
  17. Sam Gorman, Kirstie Rickaby, Li Lu, Christopher J. Kiely, Donald E. Macphee, Andrea Folli. A Combination of EPR, Microscopy, Electrophoresis and Theory to Elucidate the Chemistry of W- and N-Doped TiO2 Nanoparticle/Water Interfaces. Catalysts 2021, 11 (11) , 1305.
  18. Xiaoyu Wu, Qiaoling Li, Xuewei Wang, Zhi Xie, Xiaojing Yang, Xiaofei Yu, Xinghua Zhang, Zunming Lu, Lanlan Li. Pd nanoparticles loaded onto a TiO 2 –C heterostructure via a photochemical strategy for efficient oxygen reduction reaction. New Journal of Chemistry 2021, 45 (39) , 18379-18386.
  19. Ilgar Ayyubov, Irina Borbáth, Zoltán Pászti, Zoltán Sebestyén, Judith Mihály, Tamás Szabó, Erzsébet Illés, Attila Domján, Mihaela Florea, Dana Radu, Andrei Kuncser, András Tompos, Emília Tálas. Synthesis and Characterization of Graphite Oxide Derived TiO2-Carbon Composites as Potential Electrocatalyst Supports. Topics in Catalysis 2021, 281
  20. Debashis Mahato, Yashwant Pratap Kharwar, Kothandaraman Ramanujam, Prathap Haridoss, Tiju Thomas. S, N co-doped graphene quantum dots decorated TiO2 and supported with carbon for oxygen reduction reaction catalysis. International Journal of Hydrogen Energy 2021, 46 (41) , 21549-21565.
  21. Di Pang, Yue Liu, Haiou Song, Duozhe Chen, Weiqing Zhu, Rumeng Liu, Hu Yang, Aimin Li, Shupeng Zhang. Trace Ti3+- and N-codoped TiO2 nanotube array anode for significantly enhanced electrocatalytic degradation of tetracycline and metronidazole. Chemical Engineering Journal 2021, 405 , 126982.
  22. Jihai Duan, Peng Pan, Kang Xue, Hui Zhao, Zisheng Zhang, Weiwen Wang. Energy band regulation and heterophase surface heterojunction in B-C-N-TiO2 catalysts for enhanced photocatalytic activity. Applied Nanoscience 2020, 10 (12) , 4415-4426.
  23. Shushu Chu, Hui Li, Qian Ma, Hang Li, Jia Guo, Qi Zhang. MOF/TBOT-derived hierarchical C-N/Co/Ti composites with effective elemental separation for enhanced oxygen reduction reaction. Applied Surface Science 2020, 514 , 145953.
  24. Arpita Jana, Duncan H. Gregory. Microwave‐Assisted Synthesis of ZnO–rGO Core–Shell Nanorod Hybrids with Photo‐ and Electro‐Catalytic Activity. Chemistry – A European Journal 2020, 26 (29) , 6703-6714.
  25. Zhu Gao, Jiaxing Wang, Yaseen Muhammad, Yibo Zhang, Syed Jalil Shah, Yang Hu, Zhe Chu, Zhongxing Zhao, Zhenxia Zhao. Enhanced moisture-resistance and excellent photocatalytic performance of synchronous N/Zn-decorated MIL-125(Ti) for vaporous acetaldehyde degradation. Chemical Engineering Journal 2020, 388 , 124389.
  26. Weiliang Qi, Xiangjian Meng, Samira Adimi, Haichuan Guo, Tiju Thomas, Fei Li, Heng Jiang, Siqi Liu, Minghui Yang. A size tunable bimetallic nickel-zinc nitride as a multi-functional co-catalyst on nitrogen doped titania boosts solar energy conversion. Dalton Transactions 2020, 49 (15) , 4887-4895.
  27. Likun Wang, Stoyan Bliznakov, Rebecca Isseroff, Yuchen Zhou, Xianghao Zuo, Aniket Raut, Wanhua Wang, Michael Cuiffo, Taejin Kim, Miriam H. Rafailovich. Enhancing proton exchange membrane fuel cell performance via graphene oxide surface synergy. Applied Energy 2020, 261 , 114277.
  28. Likun Wang, Xianghao Zuo, Aniket Raut, Rebecca Isseroff, Yuan Xue, Yuchen Zhou, Bhawan Sandhu, Tzipora Schein, Tatiana Zeliznyak, Priyanka Sharma, Sunil Sharma, Benjamin S. Hsiao, Miriam H. Rafailovich. Operation of proton exchange membrane (PEM) fuel cells using natural cellulose fiber membranes. Sustainable Energy & Fuels 2019, 3 (10) , 2725-2732.
  29. Xiaojing Lin, Mingxuan Sun, Shanfu Sun, Zizhong Zhang. Graphene promoted triphasic N/Ti3+-TiO2 heterostructures: In-situ hydrothermal synthesis and enhanced photocatalytic performance. Journal of Alloys and Compounds 2019, 785 , 732-741.
  30. Xin Tong, G. Zhang, Jai Prakash, Shuhui Sun. 3D Graphene and Its Nanocomposites: From Synthesis to Multifunctional Applications. 2019,,, 363-388.
  31. Alison Fraser, Zishuai Zhang, Geraldine Merle, Uwe Gbureck, Siyu Ye, Jeff Gostick, Jake Barralet. Composite Carbon Nanotube Microsphere Coatings for Use as Electrode Supports. Advanced Functional Materials 2018, 28 (46) , 1803713.
  32. Vittal Sharavath, Suprabhat Sarkar, Sutapa Ghosh. One-pot hydrothermal synthesis of TiO2/graphene nanocomposite with simultaneous nitrogen-doping for energy storage application. Journal of Electroanalytical Chemistry 2018, 829 , 208-216.
  33. Minggui Wang, Huan Zhang, Huali Zu, Zhengrong Zhang, Jie Han. Construction of TiO2/CdS heterojunction photocatslysts with enhanced visible light activity. Applied Surface Science 2018, 455 , 729-735.
  34. Baharak Ayoubi-Feiz, Mohammad Hossein Mashhadizadeh, Mohsen Sheydaei. Preparation of reusable nano N-TiO2/graphene/titanium grid sheet for electrosorption-assisted visible light photoelectrocatalytic degradation of a pesticide: Effect of parameters and neural network modeling. Journal of Electroanalytical Chemistry 2018, 823 , 713-722.
  35. Bei-Hua Hou, Qiang Wang, Wen-Chao Lu, Yao Xiao, Hai-Xia Zhang, Min-Ji Liao, Zi-Chun Zhu, Ping Chen. Bulk Production of Non-Precious Metal Catalysts with High Surface Area and Excellent Activity in the Oxygen Reduction Reaction. ChemElectroChem 2018, 5 (14) , 1854-1861.
  36. Tuo Ji, Rui Tu, Licheng Li, Liwen Mu, Chang Liu, Xiaohua Lu, Jiahua Zhu. Localizing microwave heat by surface polarization of titanate nanostructures for enhanced catalytic reaction efficiency. Applied Catalysis B: Environmental 2018, 227 , 266-275.
  37. Yuanyuan Chu, Ning Zhang, Jingjing Yang, Haitao Wang, Zhao Dai, Liang Wang, Jun Gao, Xiaoyao Tan. Designed synthesis of thin CeO2 nanowires-supported Pt electrocatalysts with pore-interconnected structure and its high catalytic activity for methanol oxidation. Journal of Materials Science 2018, 53 (3) , 2087-2101.
  38. Peng Zhang, Qiang Hu, Xuejing Yang, Xiuli Hou, Jianli Mi, Lei Liu, Mingdong Dong. Size effect of oxygen reduction reaction on nitrogen-doped graphene quantum dots. RSC Advances 2018, 8 (1) , 531-536.
  39. Chuansheng Chen, Wei Mei, Weiwei Yu, Xi'an Chen, Longhui Zeng, Yuenhong Tsang, Zisheng Chao, Xiaoyan Liu. Enhanced sunlight-driven photocatalytic property of Mg-doped ZnO nanocomposites with three-dimensional graphene oxide/MoS 2 nanosheet composites. RSC Advances 2018, 8 (31) , 17399-17409.
  40. N.R. Khalid, A. Majid, M. Bilal Tahir, N.A. Niaz, Sadia Khalid. Carbonaceous-TiO2 nanomaterials for photocatalytic degradation of pollutants: A review. Ceramics International 2017, 43 (17) , 14552-14571.
  41. Xin Tong, Qiliang Wei, Xinxing Zhan, Gaixia Zhang, Shuhui Sun. The New Graphene Family Materials: Synthesis and Applications in Oxygen Reduction Reaction. Catalysts 2017, 7 (12) , 1.
  42. Haitao Wang, Yu Xue, Baohui Zhu, Jingjing Yang, Liang Wang, Xiaoyao Tan, Zhenbo Wang, Yuanyuan Chu. CeO 2 nanowires stretch-embedded in reduced graphite oxide nanocomposite support for Pt nanoparticles as potential electrocatalyst for methanol oxidation reaction. International Journal of Hydrogen Energy 2017, 42 (32) , 20549-20559.
  43. Yiren Lian, Wenkun Zhu, Weitang Yao, Huan Yi, Zuowen Hu, Tao Duan, Wencai Cheng, Xianfeng Wei, Guozhen Hu. A biomass carbon mass coated with modified TiO 2 nanotube/graphene for photocatalysis. New Journal of Chemistry 2017, 41 (10) , 4212-4219.
  44. Dong-Dong Qin, Qiu-Hong Wang, Jing Chen, Cai-Hua He, Yang Li, Cai-He Wang, Jing-Jing Quan, Chun-Lan Tao, Xiao-Quan Lu. Phosphorus-doped TiO 2 nanotube arrays for visible-light-driven photoelectrochemical water oxidation. Sustainable Energy & Fuels 2017, 1 (2) , 248-253.
  45. P. Dhanasekaran, S. Vinod Selvaganesh, Santoshkumar D. Bhat. Enhanced catalytic activity and stability of copper and nitrogen doped titania nanorod supported Pt electrocatalyst for oxygen reduction reaction in polymer electrolyte fuel cells. New J. Chem. 2017, 41 (21) , 13012-13026.
  46. Wenjing Yuan, Anjian Xie, Shikuo Li, Fangzhi Huang, Peigen Zhang, Yuhua Shen. High-activity oxygen reduction catalyst based on low-cost bagasse, nitrogen and large specific surface area. Energy 2016, 115 , 397-403.
  47. D. Hassen, M.A. Shenashen, S.A. El-Safty, M.M. Selim, H. Isago, A. Elmarakbi, A. El-Safty, H. Yamaguchi. Nitrogen-doped carbon-embedded TiO2 nanofibers as promising oxygen reduction reaction electrocatalysts. Journal of Power Sources 2016, 330 , 292-303.
  48. Wen-Yuan Yan, Qi Zhou, Xing Chen, Xing-Jiu Huang, Yu-Cheng Wu. C-doped and N-doped reduced graphene oxide/TiO2 composites with exposed (0 0 1) and (1 0 1) facets controllably synthesized by a hydrothermal route and their gas sensing characteristics. Sensors and Actuators B: Chemical 2016, 230 , 761-772.
  49. Jiamian Wang, Xiuyun Wang, Shuo Wu, Jie Song, Yanqiu Zhao, Yanqiu Ge, Changgong Meng. Fabrication of highly catalytic silver nanoclusters/graphene oxide nanocomposite as nanotag for sensitive electrochemical immunoassay. Analytica Chimica Acta 2016, 906 , 80-88.
  50. Xing Zhang, Yongan Hu, Daozheng Zhu, Anjian Xie, Yuhua Shen. A novel porous CuO nanorod/rGO composite as a high stability anode material for lithium-ion batteries. Ceramics International 2016, 42 (1) , 1833-1839.
  51. Zipeng Xing, Zhenzi Li, Xiaoyan Wu, Guofeng Wang, Wei Zhou. In-situ S-doped porous anatase TiO2 nanopillars for high-efficient visible-light photocatalytic hydrogen evolution. International Journal of Hydrogen Energy 2016, 41 (3) , 1535-1541.
  52. Chao Liu, Liqiang Zhang, Rui Liu, Zhenfei Gao, Xiaopeng Yang, Zhiqiang Tu, Fan Yang, Zhizhen Ye, Lishan Cui, Chunming Xu, Yongfeng Li. Hydrothermal synthesis of N-doped TiO 2 nanowires and N-doped graphene heterostructures with enhanced photocatalytic properties. Journal of Alloys and Compounds 2016, 656 , 24-32.
  53. Wenjing Yuan, Yi Feng, Anjian Xie, Xiuzhen Zhang, Fangzhi Huang, Shikuo Li, Xing Zhang, Yuhua Shen. Nitrogen-doped nanoporous carbon derived from waste pomelo peel as a metal-free electrocatalyst for the oxygen reduction reaction. Nanoscale 2016, 8 (16) , 8704-8711.
  54. Guiting Xie, Bohong Chen, Zhongqing Jiang, Xiaojun Niu, Si Cheng, Zihao Zhen, Yu Jiang, Haibo Rong, Zhong-Jie Jiang. High catalytic activity of Co 3 O 4 nanoparticles encapsulated in a graphene supported carbon matrix for oxygen reduction reaction. RSC Advances 2016, 6 (55) , 50349-50357.
  55. Wenjing Yuan, Ping Chen, Anjian Xie, Shikuo Li, Fangzhi Huang, Yuhua Shen. Napkin Paper Derived Nitrogen-Doped Carbon Sheets: A High-Performance Electrocatalyst for Oxygen Reduction Reaction. Journal of The Electrochemical Society 2016, 163 (14) , H1204-H1209.
  56. Wenjing Yuan, Juchuan Li, Anjian Xie, Ping Chen, Shikuo Li, Yuhua Shen. Practical, cost-effective and large-scale production of nitrogen-doped porous carbon particles and their use as metal-free electrocatalysts for oxygen reduction. Electrochimica Acta 2015, 165 , 29-35.
  57. Xiang-Jun Huang, Ya-Nan Luan, Peng-Fei Yao, Jin-Song Xie, Liang Yu, Zhen-Yu Wu, Ping Chen. In situ formation of N- and Fe-doped carbon nanotube/mesoporous carbon nanocomposite with excellent activity for oxygen reduction in acidic media. RSC Advances 2015, 5 (93) , 76599-76606.
  58. Yuan Xia, Beibei Wang, Gang Wang, Hui Wang. Easy access to nitrogen-doped mesoporous interlinked carbon/NiO nanosheet for application in lithium-ion batteries and supercapacitors. RSC Advances 2015, 5 (120) , 98740-98746.