Abstract
Photocatalysis based on the use of semiconducting materials is an emerging alternative to conventional thermochemical catalysis, and it has the potential to promote chemical synthesis under greener and milder conditions. However, heterogeneous photocatalytic organic reactions are still in their infancy, limited by the low-efficiency carrier separation of the currently available photocatalytic materials. Here, we report photochromic Bi2WO6–x/amorphous BiOCl (p-BWO) nanosheets, which, distinct from pristine Bi2WO6, show blue colouration upon visible light irradiation and are bleached by atmospheric oxygen. Studies on the microscopic structure of the material reveal the existence of abundant W(vi)O6–x units, which serve as the sites for the fast and continuous consumption of photogenerated electrons, thereby effectively facilitating the separation of electron–hole pairs. The prepared composite features a remarkable enhancement in performance for the photocatalytic oxidation of toluene with a conversion rate 166-fold higher compared with that of pristine Bi2WO6.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Hao, C. H. et al. Visible-light-driven selective photocatalytic hydrogenation of cinnamaldehyde over Au/SiC catalysts. J. Am. Chem. Soc. 138, 9361–9364 (2016).
Huang, Y. M. et al. Stable copper nanoparticle photocatalysts for selective epoxidation of alkenes with visible light. ACS Catal. 7, 4975–4985 (2017).
Chai, Z. et al. Efficient visible light-driven splitting of alcohols into hydrogen and corresponding carbonyl compounds over a Ni-modified CdS photocatalyst. J. Am. Chem. Soc. 138, 10128–10131 (2016).
Huang, W. et al. Visible-light-promoted selective oxidation of alcohols using a covalent triazine framework. ACS Catal. 7, 5438–5442 (2017).
Zhang, N. et al. Oxide defect engineering enables to couple solar energy into oxygen activation. J. Am. Chem. Soc. 138, 8928–8935 (2016).
Ravelli, D., Dondi, D., Fagnoni, M. & Albini, A. Photocatalysis. A multi-faceted concept for green chemistry. Chem. Soc. Rev. 38, 1999–2011 (2009).
Yu, Z. et al. Photocatalytic hydrogenation of nitroarenes using Cu1.94S–Zn0.23Cd0.77S heteronanorods. Nano Res. 11, 3730–3738 (2018).
Nicewicz, D. A. & MacMillan, D. W. Merging photoredox catalysis with organocatalysis: the direct asymmetric alkylation of aldehydes. Science 322, 77–80 (2008).
Huo, H. et al. Asymmetric photoredox transition-metal catalysis activated by visible light. Nature 515, 100–103 (2014).
Gao, C., Wang, J., Xu, H. & Xiong, Y. Coordination chemistry in the design of heterogeneous photocatalysts. Chem. Soc. Rev. 46, 2799–2823 (2017).
Marschall, R. Semiconductor composites: strategies for enhancing charge carrier separation to improve photocatalytic activity. Adv. Funct. Mater. 24, 2421–2440 (2014).
Huang, J. et al. Oxyhydroxide nanosheets with highly efficient electron–hole pair separation for hydrogen evolution. Angew. Chem. Int. Ed. Engl. 55, 2137–2141 (2016).
Pan, X. Y. et al. Design synthesis of nitrogen-doped TiO2@carbon nanosheets toward selective nitroaromatics reduction under mild conditions. ACS Catal. 7, 6991–6998 (2017).
Fu, Y. S., Huang, T., Jia, B. Q., Zhu, J. W. & Wang, X. Reduction of nitrophenols to aminophenols under concerted catalysis by Au/g–C3N4 contact system. Appl. Catal. B 202, 430–437 (2017).
Yuan, R. et al. Chlorine-radical-mediated photocatalytic activation of C–H bonds with visible light. Angew. Chem. Int. Ed. Engl. 52, 1035–1039 (2013).
Tripathy, J., Lee, K. & Schmuki, P. Tuning the selectivity of photocatalytic synthetic reactions using modified TiO2 nanotubes. Angew. Chem. Int. Ed. Engl. 53, 12605–12608 (2014).
Yu, S., Kim, Y. H., Lee, S. Y., Song, H. D. & Yi, J. Hot-electron-transfer enhancement for the efficient energy conversion of visible light. Angew. Chem. Int. Ed. Engl. 53, 11203–11207 (2014).
Li, H. J., Zhou, Y., Tu, W. G., Ye, J. H. & Zou, Z. G. State-of-the-art progress in diverse heterostructured photocatalysts toward promoting photocatalytic performance. Adv. Funct. Mater. 25, 998–1013 (2015).
Li, J., Dong, Xa, Sun, Y., Cen, W. & Dong, F. Facet-dependent interfacial charge separation and transfer in plasmonic photocatalysts. Appl. Catal. B 226, 269–277 (2018).
Chen, Y. et al. Synergetic integration of Cu1.94S–ZnxCd1– xS heteronanorods for enhanced visible-light-driven photocatalytic hydrogen production. J. Am. Chem. Soc. 138, 4286–4289 (2016).
Xiang, Q., Cheng, B. & Yu, J. Graphene-based photocatalysts for solar-fuel generation. Angew. Chem. Int. Ed. Engl. 54, 11350–11366 (2015).
Yuan, Y.-P., Ruan, L.-W., Barber, J., Joachim Loo, S. C. & Xue, C. Hetero-nanostructured suspended photocatalysts for solar-to-fuel conversion. Energy Environ. Sci. 7, 3934–3951 (2014).
Yan, P. et al. Photovoltaic device based on TiO2 rutile/anatase phase junctions fabricated in coaxial nanorod arrays. Nano Energy 15, 406–412 (2015).
Low, J., Yu, J., Jaroniec, M., Wageh, S. & Al-Ghamdi, A. A. Heterojunction photocatalysts. Adv. Mater. 29, 1601694 (2017).
Kesavan, L. et al. Solvent-free oxidation of primary carbon–hydrogen bonds in toluene using Au–Pd alloy nanoparticles. Science 331, 195–199 (2011).
Zhou, Y. et al. Monolayered Bi2WO6 nanosheets mimicking heterojunction interface with open surfaces for photocatalysis. Nat. Commun. 6, 8340 (2015).
Nie, Z.-P., Ma, D.-K., Fang, G.-Y., Chen, W. & Huang, S.-M. Concave Bi2WO6 nanoplates with oxygen vacancies achieving enhanced electrocatalytic oxygen evolution in near-neutral water. J. Mater. Chem. A 4, 2438–2444 (2016).
Yao, J. N., Hashimoto, K. & Fujishima, A. Photochromism induced in an electrolytically pretreated MoO3 thin-film by visible-light. Nature 355, 624–626 (1992).
He, T. & Yao, J. N. Photochromic materials based on tungsten oxide. J. Mater. Chem. 17, 4547–4557 (2007).
Bi, W. et al. Molecular co-catalyst accelerating hole transfer for enhanced photocatalytic H2 evolution. Nat. Commun. 6, 8647 (2015).
Zhang, W. et al. Selective aerobic oxidation reactions using a combination of photocatalytic water oxidation and enzymatic oxyfunctionalizations. Nat. Catal. 1, 55–62 (2018).
Kaeding, W. W., Lindblom, R. O., Temple, R. G. & Mahon, H. I. Oxidation of toluene and other alkylated aromatic hydrocarbons to benzoic acids and phenols. Ind. Eng. Chem. Process Des. Dev. 4, 97–101 (1965).
Li, H. et al. New reaction pathway induced by plasmon for selective benzyl alcohol oxidation on BiOCl possessing oxygen vacancies. J. Am. Chem. Soc. 139, 3513–3521 (2017).
Zhang, Z. et al. A nonmetal plasmonic Z-scheme photocatalyst with UV- to NIR-driven photocatalytic protons reduction. Adv. Mater. 29, 1606688–1606696 (2017).
Lou, Z. et al. Continual injection of photoinduced electrons stabilizing surface plasmon resonance of non-elemental-metal plasmonic photocatalyst CdS/WO3−x for efficient hydrogen generation. Appl. Catal. B 226, 10–15 (2018).
Li, H., Li, J., Ai, Z., Jia, F. & Zhang, L. Oxygen vacancy-mediated photocatalysis of BiOCl: reactivity, selectivity, and perspectives. Angew. Chem. Int. Ed. Engl. 57, 122–138 (2018).
Zhang, N., Ciriminna, R., Pagliaro, M. & Xu, Y. J. Nanochemistry-derived Bi2WO6 nanostructures: towards production of sustainable chemicals and fuels induced by visible light. Chem. Soc. Rev. 43, 5276–5287 (2014).
Li, J., Yu, Y. & Zhang, L. Bismuth oxyhalide nanomaterials: layered structures meet photocatalysis. Nanoscale 6, 8473–8488 (2014).
Cheng, H. et al. An anion exchange approach to Bi2WO6 hollow microspheres with efficient visible light photocatalytic reduction of CO2 to methanol. Chem. Commun. 48, 9729–9731 (2012).
Zhang, J., Wang, T., Chang, X., Li, A. & Gong, J. Fabrication of porous nanoflake BiMOx (M = W, V, and Mo) photoanodes via hydrothermal anion exchange. Chem. Sci. 7, 6381–6386 (2016).
Ma, Y. C., Chen, Z. W., Qu, D. & Shi, J. S. Synthesis of chemically bonded BiOCl@Bi2WO6 microspheres with exposed (020) Bi2WO6 facets and their enhanced photocatalytic activities under visible light irradiation. Appl. Surf. Sci. 361, 63–71 (2016).
Guan, M. et al. Vacancy associates promoting solar-driven photocatalytic activity of ultrathin bismuth oxychloride nanosheets. J. Am. Chem. Soc. 135, 10411–10417 (2013).
Santos, V. P., Bakker, J. J. W., Kreutzer, M. T., Kapteijn, F. & Gascon, J. Transport limitations during phase transfer catalyzed ethyl-benzene oxidation: facts and fictions of “halide catalysis”. ACS Catal. 2, 1421–1424 (2012).
Santato, C., Odziemkowski, M., Ulmann, M. & Augustynski, J. Crystallographically oriented mesoporous WO3 films: synthesis, characterization, and applications. J. Am. Chem. Soc. 123, 10639–10649 (2001).
Arnoldussen, T. C. A model for electrochromic tungstic oxide microstructure and degradation. J. Electrochem. Soc. 128, 117–123 (1981).
Yang, Y. A., M., Y., Yao, J. N. & Loo, B. H. Simulation of the sublimation process in the preparation of photochromic WO3 film by laser microprobe mass spectrometry. J. Non-Cryst. Solids 272, 71–74 (2000).
Shi, R., Huang, G., Lin, J. & Zhu, Y. Photocatalytic activity enhancement for Bi2WO6 by fluorine substitution. J. Phys. Chem. C 113, 19633–19638 (2009).
Kongmark, C. et al. A comprehensive scenario of the crystal growth of gamma-Bi2MoO6 catalyst during hydrothermal synthesis. Cryst. Growth Des. 12, 5994–6003 (2012).
Kleperis, J. J., Cikmach, P. D. & Lusis, A. R. Colour centres in amorphous tungsten trioxide thin films. Phys. Status Solidi A 83, 291–297 (1984).
Wu, Q. et al. Ultra-small yellow defective TiO2 nanoparticles for co-catalyst free photocatalytic hydrogen production. Nano Energy 24, 63–71 (2016).
Acknowledgements
This work was supported by the National Key R&D Program of China (2017YFA0700101 and 2016YFA0202801) and National Natural Science Foundation of China (numbers 21325101, 21231005, 21573119 and 21590792). We thank the 1W1B station for XAFS measurements at the Beijing Synchrotron Radiation Facility.
Author information
Authors and Affiliations
Contributions
X.C., Z.C., R.L., W-C.C., S.L. and J.Z. performed the experimental work and analysed the results. T.H., X.T., Y.W., R.S., D.W. and W.Z. discussed and provided advice on the work. X.C., Z.C., Q.P., C.C. and Y.L. conceived and designed the experiments. All authors co-wrote the manuscript.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Supplementary Information
Supplementary Methods; Supplementary Tables 1–6; Supplementary Figures 1–33; Supplementary Note; Supplementary References
Rights and permissions
About this article
Cite this article
Cao, X., Chen, Z., Lin, R. et al. A photochromic composite with enhanced carrier separation for the photocatalytic activation of benzylic C–H bonds in toluene. Nat Catal 1, 704–710 (2018). https://doi.org/10.1038/s41929-018-0128-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41929-018-0128-z