Abstract
High-efficiency photocatalysts are of great importance to satisfy the requirements of green chemistry nowadays. Here we reported a novel solar-driven photocatalyst fabricated by a facile surface modification method, with the two-dimensional carboxylated zinc phthalocyanine-carboxylated C60-titanium dioxide (ZnPc-C3-TiO2) nanosheets, in which the surface modifications of ZnPc and C60 derivative were designed to extend the absorption range and promote charge separation, respectively. Benefiting from the unique structure and positive synergetic effect, the ZnPc-C3-TiO2 nanocomposite shows promising applications in selective reduction of nitroarenes for high-value-added aromatic amines under solar light. Especially, for the photocatalytic reduction of nitrobenzene to aniline, the ZnPc-C3-TiO2 nanocomposite possesses both high efficiency and selectivity (up to 99%).
摘要
高效的光催化剂对于满足当今绿色化学的发展具有特别重 要的意义. 本文采用表面修饰法, 制备了一种二维羧基锌酞菁-羧基 C60-二氧化钛(ZnPc-C3-TiO2)纳米片, 其中表面修饰的ZnPc和C60衍 生物分别用于扩展太阳光的吸收范围和促进光生电荷分离. 得益 于其独特的结构和良好的协同效应, ZnPc-C3-TiO2纳米复合材料 在太阳光下选择性光催化芳香硝基化合物还原为芳香胺的反应中 显示出良好的应用前景. 特别地, 对于光催化硝基苯还原为苯胺的 反应, ZnPc-C3-TiO2复合材料同时表现出较高的催化转化效率和选 择性(均高达99%).
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Cheng L, Li X, Zhang H, et al. Two-dimensional transition metal MXene-based photocatalysts for solar fuel generation. J Phys Chem Lett, 2019, 10: 3488–3494
Zhao Z, Xing Y, Li H, et al. Constructing CdS/Cd/doped TiO2 Z-scheme type visible light photocatalyst for H2 production. Sci China Mater, 2018, 61: 851–860
Xu Q, Cheng B, Yu J, et al. Making co-condensed amorphous carbon/g-C3N4 composites with improved visible-light photocatalytic H2-production performance using Pt as cocatalyst. Carbon, 2017, 118: 241–249
Cao S, Shen B, Tong T, et al. 2D/2D heterojunction of ultrathin MXene/Bi2WO6 nanosheets for improved photocatalytic CO2 reduction. Adv Funct Mater, 2018, 28: 1800136
Richardson RD, Holland EJ, Carpenter BK. A renewable amine for photochemical reduction of CO2. Nat Chem, 2011, 3: 301–303
Gao C, Meng Q, Zhao K, et al. Co3O4 hexagonal platelets with controllable facets enabling highly efficient visible-light photocatalytic reduction of CO2. Adv Mater, 2016, 28: 6485–6490
Zhao K, Zhao S, Gao C, et al. Metallic cobalt-carbon composite as recyclable and robust magnetic photocatalyst for efficient CO2 reduction. Small, 2018, 14: 1800762
Wu H, Mei S, Cao X, et al. Facile synthesis of Pt/Pd nanodendrites for the direct oxidation of methanol. Nanotechnology, 2014, 25: 195702
Liu L, Liu H, Zhao YP, et al. Directed synthesis of hierarchical nanostructured TiO2 catalysts and their morphology-dependent photocatalysis for phenol degradation. Environ Sci Technol, 2008, 42: 2342–2348
Shiraishi Y, Togawa Y, Tsukamoto D, et al. Highly efficient and selective hydrogenation of nitroaromatics on photoactivated rutile titanium dioxide. ACS Catal, 2012, 2: 2475–2481
Fan Y, Hu G, Yu S, et al. Recent advances in TiO2 nanoarrays/graphene for water treatment and energy conversion/storage. Sci China Mater, 2018, 62: 325–340
Liu X, Xing Z, Zhang Y, et al. Fabrication of 3D flower-like black N-TiO2−x@MoS2 for unprecedented-high visible-light-driven photocatalytic performance. Appl Catal B-Environ, 2017, 201: 119–127
Pan X, Yang MQ, Fu X, et al. Defective TiO2 with oxygen vacancies: Synthesis, properties and photocatalytic applications. Nanoscale, 2013, 5: 3601–3614
Fang W, Xing M, Zhang J. A new approach to prepare Ti3+ self-doped TiO2via NaBH4 reduction and hydrochloric acid treatment. Appl Catal B-Environ, 2014, 160–161: 240–246
Zhao K, Zhao S, Qi J, et al. Cu2O clusters grown on TiO2 nanoplates as efficient photocatalysts for hydrogen generation. Inorg Chem Front, 2016, 3: 488–493
Yang MQ, Zhang N, Xu YJ. Synthesis of fullerene-, carbon nanotube-, and graphene-TiO2 nanocomposite photocatalysts for selective oxidation: A comparative study. ACS Appl Mater Interfaces, 2013, 5: 1156–1164
Wang S, Liu C, Dai K, et al. Fullerene C70-TiO2 hybrids with enhanced photocatalytic activity under visible light irradiation. J Mater Chem A, 2015, 3: 21090–21098
Meng ZD, Zhu L, Choi JG, et al. Effect of Pt treated fullerene/TiO2 on the photocatalytic degradation of MO under visible light. J Mater Chem, 2011, 21: 7596–7603
Zhang L, Wang Y, Xu T, et al. Surface hybridization effect of C60 molecules on TiO2 and enhancement of the photocatalytic activity. J Mol Catal A-Chem, 2010, 331: 7–14
Chai B, Liao X, Song F, et al. Fullerene modified C3N4 composites with enhanced photocatalytic activity under visible light irradiation. Dalton Trans, 2014, 43: 982–989
Meng ZD, Peng MM, Zhu L, et al. Fullerene modification CdS/TiO2 to enhancement surface area and modification of photocatalytic activity under visible light. Appl Catal B-Environ, 2012, 113–114: 141–149
Bilal Tahir M, Nabi G, Rafique M, et al. Role of fullerene to improve the WO3 performance for photocatalytic applications and hydrogen evolution. Int J Energy Res, 2018, 42: 4783–4789
Meng ZD, Zhu L, Choi JG, et al. Preparation, characterization and photocatalytic behavior of WO3-fullerene/TiO2 catalysts under visible light. Nanoscale Res Lett, 2011, 6: 459
Meng ZD, Ghosh T, Zhu L, et al. Synthesis of fullerene modified with Ag2S with high photocatalytic activity under visible light. J Mater Chem, 2012, 22: 16127–16135
Lee SHA, Abrams NM, Hoertz PG, et al. Coupling of titania inverse opals to nanocrystalline titania layers in dye-sensitized solar cells. J Phys Chem B, 2008, 112: 14415–14421
Wu J, Hao S, Lin J, et al. Crystal morphology of anatase titania nanocrystals used in dye-sensitized solar cells. Cryst Growth Des, 2008, 8: 247–252
Wan Y, Cong T, Liang Q, et al. Facile in-situ solvothermal method to synthesize ZnPc-MWCNTs composites with enhanced visible light photocatalytic activity. Ceramics Int, 2016, 42: 2425–2430
Zhang M, Shao C, Guo Z, et al. Hierarchical nanostructures of copper(II) phthalocyanine on electrospun TiO2 nanofibers: Controllable solvothermal-fabrication and enhanced visible photocatalytic properties. ACS Appl Mater Interfaces, 2011, 3: 369–377
Reddy P, Giribabu L, Lyness C, et al. Efficient sensitization of nanocrystalline TiO2 films by a near-IR-absorbing unsymmetrical zinc phthalocyanine. Angew Chem, 2007, 119: 377–380
He J, Benkö G, Korodi F, et al. Modified phthalocyanines for efficient near-IR sensitization of nanostructured TiO2 electrode. J Am Chem Soc, 2002, 124: 4922–4932
Lamparth I, Hirsch A. Water-soluble malonic acid derivatives of C60 with a defined three-dimensional structure. J Chem Soc Chem Commun, 1994, 14: 1727–1728
Han X, Kuang Q, Jin M, et al. Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties. J Am Chem Soc, 2009, 131: 3152–3153
Bai M, Song R, Zhang Y, et al. Trimellitic anhydride- and pyromellitic dianhydride-originated tetrakis/octakis(octyloxycarbonyl) phthalocyaninato metal complexes. InOrg Chem Commun, 2013, 28: 99–103
Grinter DC, Woolcot T, Pang CL, et al. Ordered carboxylates on TiO2 (110) formed at aqueous interfaces. J Phys Chem Lett, 2014, 5: 4265–4269
Yang K, Chen X, Zheng Z, et al. Solvent-induced surface disorder and doping-induced lattice distortion in anatase TiO2 nanocrystals for enhanced photoreversible color switching. J Mater Chem A, 2019, 7: 3863–3873
Liu W, Liu Z, Wang G, et al. Carbon coated Au/TiO2 mesoporous microspheres: A novel selective photocatalyst. Sci China Mater, 2017, 60: 438–448
Yu J, Ma T, Liu G, et al. Enhanced photocatalytic activity of bimodal mesoporous titania powders by C60 modification. Dalton Trans, 2011, 40: 6635–6644
Li B, Zhao Z, Gao F, et al. Mesoporous microspheres composed of carbon-coated TiO2 nanocrystals with exposed {001} facets for improved visible light photocatalytic activity. Appl Catal B-Environ, 2014, 147: 958–964
Zhang P, Shao C, Zhang Z, et al. TiO2@carbon core/shell nanofibers: controllable preparation and enhanced visible photocatalytic properties. Nanoscale, 2011, 3: 2943–2949
Lin J, Zong R, Zhou M, et al. Photoelectric catalytic degradation of methylene blue by C60-modified TiO2 nanotube array. Appl Catal B-Environ, 2009, 89: 425–431
Max JJ, Chapados C. Infrared spectroscopy of aqueous carboxylic acids: Comparison between different acids and their salts. J Phys Chem A, 2004, 108: 3324–3337
Qian W, Wei W, Hong M, et al. Microwave assisted synthesis of ZnPc-COOH and SiO2/ZnPc-COOH nanopaticles: Singlet oxygen production and photocatalytic property. Colloids Surfs A-Physicochem Eng Aspects, 2014, 443: 52–59
Xu H. Synthesis of novel amphiphilic zinc phthalocyanines and fabrication of zinc phthalocyanine-titanium oxide multilayers. Dyes Pigments, 2001, 49: 9–14
Hamandi M, Berhault G, Guillard C, et al. Reduced graphene oxide/TiO2 nanotube composites for formic acid photodegradation. Appl Catal B-Environ, 2017, 209: 203–213
Zhang X, Yu L, Li R, et al. Asymmetry and electronic directionality: A means of improving the red/near-IR-light-responsive photoactivity of phthalocyanine-sensitized carbon nitride. Catal Sci Technol, 2014, 4: 3251
Li K, Lin L, Peng T, et al. Asymmetric zinc porphyrin-sensitized nanosized TiO2 for efficient visible-light-driven CO2 photoreduction to CO/CH4. Chem Commun, 2015, 51: 12443–12446
Huang Z, Zheng B, Zhu S, et al. Photocatalytic activity of phthalocyanine-sensitized TiO2-SiO2 microparticles irradiated by visible light. Mater Sci Semicond Process, 2014, 25: 148–152
Verho O, Nagendiran A, Tai CW, et al. Nanopalladium on aminofunctionalized mesocellular foam as an efficient and recyclable catalyst for the selective transfer hydrogenation of nitroarenes to anilines. ChemCatChem, 2014, 6: 205–211
Nazeeruddin MK, Humphry-baker R, Grätzel M, et al. Efficient near-IR sensitization of nanocrystalline TiO2 films by zinc and aluminum phthalocyanines. J Porphyrins Phthalocyanines, 2012, 03: 230–237
Hernández-Gordillo A, Romero AG, Tzompantzi F, et al. Kinetic study of the 4-nitrophenol photooxidation and photoreduction reactions using CdS. Appl Catal B-Environ, 2014, 144: 507–513
Wang E, Yang W, Cao Y. Unique surface chemical species on indium doped TiO2 and their effect on the visible light photocatalytic activity. J Phys Chem C, 2009, 113: 20912–20917
Long Y, Lu Y, Huang Y, et al. Effect of C60 on the photocatalytic activity of TiO2 nanorods. J Phys Chem C, 2009, 113: 13899–13905
Cho EC, Ciou JH, Zheng JH, et al. Fullerene C70 decorated TiO2 nanowires for visible-light-responsive photocatalyst. Appl Surf Sci, 2015, 355: 536–546
Pompa PP, Ciccarella G, Spadavecchia J, et al. Spectroscopic investigation of inner filter effects by phthalocyanine solutions. J Photochem Photobiol A-Chem, 2004, 163: 113–120
Giribabu L, Vijay Kumar C, Gopal Reddy V, et al. Unsymmetrical alkoxy zinc phthalocyanine for sensitization of nanocrystalline TiO2 films. Sol Energy Mater Sol Cells, 2007, 91: 1611–1617
Kc CB, Stranius K, D’Souza P, et al. Sequential photoinduced energy and electron transfer directed improved performance of the supramolecular solar cell of a zinc porphyrin-zinc phthalocyanine conjugate modified TiO2 surface. J Phys Chem C, 2013, 117: 763–773
Zhang L, He X, Xu X, et al. Highly active TiO2/g-C3N4/G photocatalyst with extended spectral response towards selective reduction of nitrobenzene. Appl Catal B-Environ, 2017, 203: 1–8
Hou JH, Lan X, Shi J, et al. A mild and simple method to fabricate commercial TiO2 (P25) and C60 composite for highly enhancing H2 generation. Int J Hydrogen Energy, 2020, 45: 2852–2861
Li Q, Hou X, Fang Z, et al. Construction of layered h-BN/TiO2 hetero-structure and probing of the synergetic photocatalytic effect. Sci China Mater, 2019, 63: 276–287
Yu Z, Chen Z, Chen Y, et al. Photocatalytic hydrogenation of nitroarenes using Cu1.94S-Zn0.23Cd0.77S heteronanorods. Nano Res, 2018, 11: 3730–3738
Zhang Y, Tang ZR, Fu X, et al. TiO2-graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant: Is TiO2-graphene truly different from other TiO2-carbon composite materials? ACS Nano, 2010, 4: 7303–7314
Song Y, Wang H, Wang Z, et al. Selective photocatalytic synthesis of haloanilines from halonitrobenzenes over multifunctional AuPt/monolayer titanate nanosheet. ACS Catal, 2018, 8: 9656–9664
Fukui M, Koshida W, Tanaka A, et al. Photocatalytic hydrogenation of nitrobenzenes to anilines over noble metal-free TiO2 utilizing methylamine as a hydrogen donor. Appl Catal B-Environ, 2020, 268: 118446
Ji Y, Fan T, Luo Y First-principles study on the mechanism of photocatalytic reduction of nitrobenzene on the rutile TiO2 (110) surface Phys Chem Chem Phys, 2020, 22: 1187–1193
Acknowledgements
This work was supported by Beijing Natural Science Foundation (2182094), and the National Natural Science Foundation of China (51772300 and 51832008). Wu B particularly thanks the Youth Innovation Promotion Association of CAS (2018039) We also thank Jianlei Tian for assistance in synthesis, and Jing Wan for assistance in AFM measurement.
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Liu L, Wu B and Wang C designed and engineered the experiments; Wang C and Wu B provided insights on the experiments and supervised the research; Liu L synthesized and characterized the samples; Liu X contributed to the theoretical analysis; Liu L, Chai Y and Liu X participated in the data analysis; Liu L wrote the paper with support from Wang C and Wu B. All authors contributed to the general discussion.
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Liping Liu is currently a PhD candidate at the Institute of Chemistry, Chinese Academy of Sciences. She received her MSc degree from the University of Science and Technology Beijing in 2017. Her PhD research focuses on the synthesis and design of fullerene-relevant nanomaterials and their applications in photocatalysis.
Bo Wu received her PhD degree from the Institute of Chemistry, Chinese Academy of Sciences in 2016. She worked as an assistant researcher at the Institute of Chemistry, Chinese Academy of Sciences from 2016 to 2019. She is now an associate professor at Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology. Her research focuses on the photoelectric properties of fullerene-based nanocomposites.
Chunru Wang received his PhD degree in physical chemistry in 1992 from the Chinese Academy of Sciences. Currently, he is a professor in the Institute of Chemistry, Chinese Academy of Sciences. His research interests include the synthesis, isolation, and characterization of endohedral fullerenes and the industrial applications of fullerenes and metallofullerenes.
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Surface modification of TiO2 nanosheets with fullerene and zinc-phthalocyanine for enhanced photocatalytic reduction under solar-light irradiation
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Liu, L., Liu, X., Chai, Y. et al. Surface modification of TiO2 nanosheets with fullerene and zinc-phthalocyanine for enhanced photocatalytic reduction under solar-light irradiation. Sci. China Mater. 63, 2251–2260 (2020). https://doi.org/10.1007/s40843-020-1436-5
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DOI: https://doi.org/10.1007/s40843-020-1436-5