Abstract
Photocatalytic hydrogen production coupled with selective oxidation of organic substrates to produce high-value-added fine chemicals has drawn increasing attention. Herein, we report a noble metal-free photocatalyst for the highly efficient and simultaneous generation of hydrogen and the selective oxidation of benzyl alcohol into benzaldehyde over CdS@MoS2 heterostructures under visible light. Without the need for a sacrificial agent, CdS@MoS2 displayed an excellent hydrogen production rate of 4233 µmol g−1 h−1 with 0.3 mmol benzyl alcohol, which is approximately 53 times higher than that of bare CdS nanorods (80 µmol g−1 h−1). The reaction system was highly selective for the oxidation of benzyl alcohol into benzaldehyde. When the amount of benzyl alcohol increased to 1.0 mmol, the hydrogen production reached 9033 µmol g−1 h−1. Scanning electron microscopy and transmission electron microscopy images revealed that p-type MoS2 sheets with a flower-like structure closely adhered to n-type semiconductor CdS nanorods through the formation of a p-n heterojunction. As a potential Z-scheme photocatalyst, the CdS@MoS2 heterostructure effectively produces and separates electron-hole pairs under visible light. Thus, the electrons are used for reduction to generate hydrogen, and the holes oxidize benzyl alcohol into benzaldehyde. Moreover, a mechanism of photogenerated charge transfer and separation was proposed and verified by photoluminescence, electrochemical impedance spectroscopy, photocurrent and Mott-Schottky measurements. The results reveal that the CdS@MoS2 heterojunctions have rapid and efficient charge separation and transfer, thereby greatly improving benzyl alcohol dehydrogenation. This work provides insight into the rational design of high-performance Z-scheme photocatalysts and the use of holes and electrons to obtain two valuable chemicals simultaneously.
摘要
摘要光催化产氢, 并同时选择性氧化有机底物、生产高附加值精 细化学品, 引起了科学家的广泛关注. 在本文中, 我们报道了一种无 贵金属的CdS@MoS2异质结光催化剂, 在可见光下可以高效地产氢 并同时将苯甲醇选择性氧化为苯甲醛. 在0.3 mmol苯甲醇底物的条 件下, CdS@MoS2能够产生4233 μmol g−1 h−1的氢气, 比纯的CdS纳 米棒高约53倍, 并且苯甲醇选择性氧化为苯甲醛具有很高的选择 性; 当苯甲醇增加到1.0 m mol 时, 产生氢气的量高达 9033 μmol g−1 h−1. 通过扫描电子显微镜和透射电子显微镜图像表 征, 发现p型MoS2具有花状结构并紧密粘附在n型CdS半导体纳米 棒上, 从而形成p-n异质结. 作为潜在的Z型光催化剂, CdS@MoS2 异质结催化剂在可见光下有效地产生和分离电子-空穴对, 其中电 子用于还原以产生氢气, 而空穴则将苯甲醇氧化为苯甲醛. 此外, 我们提出了光生电荷转移和分离的机理, 并通过荧光光谱、电化 学阻抗谱、光电流和莫特-肖特基测量进行了验证. 结果表明, CdS@MoS2异质结具有快速的电荷分离和转移效率, 极大地提高了 苯甲醇的脱氢性能. 这项工作为高性能Z型光催化剂的合理设计, 以及同时利用空穴和电子同时获得两种有价值的化学物质提供了 思路.
Article PDF
Similar content being viewed by others
References
Kudo A, Miseki Y. Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev, 2009, 38: 253–278
Li X, Yu J, Low J, et al. Engineering heterogeneous semiconductors for solar water splitting. J Mater Chem A, 2015, 3: 2485–2534
Lu H, Zhao J, Li L, et al. Selective oxidation of sacrificial ethanol over TiO2-based photocatalysts during water splitting. Energy Environ Sci, 2011, 4: 3384
Xu HQ, Yang S, Ma X, et al. Unveiling charge-separation dynamics in CdS/Metal-organic framework composites for enhanced photocatalysis. ACS Catal, 2018, 8: 11615–11621
Chen X, Li C, Grätzel M, et al. Nanomaterials for renewable energy production and storage. Chem Soc Rev, 2012, 41: 7909–7937
Maeda K, Teramura K, Lu D, et al. Photocatalyst releasing hydrogen from water. Nature, 2006, 440: 295
Shen L, Luo M, Liu Y, et al. Noble-metal-free MoS2 co-catalyst decorated UiO-66/CdS hybrids for efficient photocatalytic H2 production. Appl Catal B-Environ, 2015, 166–167: 445–453
Turner JA. Sustainable hydrogen production. Science, 2004, 305: 972–974
Yang MQ, Zhang N, Pagliaro M, et al. Artificial photosynthesis over graphene-semiconductor composites. Are we getting better? Chem Soc Rev, 2014, 43: 8240–8254
Liu H, Xu C, Li D, et al. Photocatalytic hydrogen production coupled with selective benzylamine oxidation over MOF composites. Angew Chem Int Ed, 2018, 57: 5379–5383
Kampouri S, Stylianou KC. Dual-functional photocatalysis for simultaneous hydrogen production and oxidation of organic substances. ACS Catal, 2019, 9: 4247–4270
Li J, Li M, Sun H, et al. Understanding of the oxidation behavior of benzyl alcohol by peroxymonosulfate via carbon nanotubes activation. ACS Catal, 2020, 10: 3516–3525
Liu Y, Zhang P, Tian B, et al. Core-shell structural CdS@SnO2 nanorods with excellent visible-light photocatalytic activity for the selective oxidation of benzyl alcohol to benzaldehyde. ACS Appl Mater Interfaces, 2015, 7: 13849–13858
Yang X, Zhao H, Feng J, et al. Visible-light-driven selective oxidation of alcohols using a dye-sensitized TiO2-polyoxometalate catalyst. J Catal, 2017, 351: 59–66
Meng S, Ye X, Zhang J, et al. Effective use of photogenerated electrons and holes in a system: Photocatalytic selective oxidation of aromatic alcohols to aldehydes and hydrogen production. J Catal, 2018, 367: 159–170
Jiang D, Chen X, Zhang Z, et al. Highly efficient simultaneous hydrogen evolution and benzaldehyde production using cadmium sulfide nanorods decorated with small cobalt nanoparticles under visible light. J Catal, 2018, 357: 147–153
Ni M, Leung MKH, Leung DYC, et al. A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production. Renew Sustain Energy Rev, 2007, 11: 401–425
Hao X, Wang Y, Zhou J, et al. Zinc vacancy-promoted photocatalytic activity and photostability of ZnS for efficient visible-light-driven hydrogen evolution. Appl Catal B-Environ, 2018, 221: 302–311
Zhu C, Liu C, Zhou Y, et al. Carbon dots enhance the stability of CdS for visible-light-driven overall water splitting. Appl Catal B-Environ, 2017, 216: 114–121
Xu Y, Zhao W, Xu R, et al. Synthesis of ultrathin CdS nanosheets as efficient visible-light-driven water splitting photocatalysts for hydrogen evolution. Chem Commun, 2013, 49: 9803–9805
Reddy DA, Kim EH, Gopannagari M, et al. Enhanced photocatalytic hydrogen evolution by integrating dual co-catalysts on heterophase CdS nano-junctions. ACS Sustain Chem Eng, 2018, 6: 12835–12844
Liu Y, Zeng C, Ai L, et al. Boosting charge transfer and hydrogen evolution performance of CdS nanocrystals hybridized with MoS2 nanosheets under visible light irradiation. Appl Surf Sci, 2019, 484: 692–700
Xu Y, Huang Y, Zhang B. Rational design of semiconductor-based photocatalysts for advanced photocatalytic hydrogen production: the case of cadmium chalcogenides. Inorg Chem Front, 2016, 3: 591–615
Jiang W, Liu Y, Zong R, et al. Photocatalytic hydrogen generation on bifunctional ternary heterostructured In2S3/MoS2/CdS composites with high activity and stability under visible light irradiation. J Mater Chem A, 2015, 3: 18406–18412
Tang ZR, Han B, Han C, et al. One dimensional CdS based materials for artificial photoredox reactions. J Mater Chem A, 2017, 5: 2387–2410
Zhang N, Liu S, Fu X, et al. Fabrication of coenocytic Pd@CdS nanocomposite as a visible light photocatalyst for selective transformation under mild conditions. J Mater Chem, 2012, 22: 5042–5052
Li YB, Li T, Dai XC, et al. Precise tuning of coordination positions for transition-metal ions via layer-by-layer assembly to enhance solar hydrogen production. ACS Appl Mater Interfaces, 2020, 12: 4373–4384
Wu K, Chen Z, Lv H, et al. Hole removal rate limits photodriven H2 generation efficiency in CdS-Pt and CdSe/CdS-Pt semiconductor nanorod-metal tip heterostructures. J Am Chem Soc, 2014, 136: 7708–7716
Liu Y, Yu YX, Zhang WD. MoS2/CdS Heterojunction with high photoelectrochemical activity for H2 evolution under visible light: The role of MoS2. J Phys Chem C, 2013, 117: 12949–12957
Zhou J, Zhang Z, Kong X, et al. A novel P-N heterojunction with staggered energy level based on ZnFe2O4 decorating SnS2 nanosheet for efficient photocatalytic degradation. Appl Surf Sci, 2020, 510: 145442
Liu Y, Niu H, Gu W, et al. In-situ construction of hierarchical CdS/MoS2 microboxes for enhanced visible-light photocatalytic H2 production. Chem Eng J, 2018, 339: 117–124
Yin XL, Li LL, Liu ML, et al. MoSx/CdS nano-heterostructures accurately constructed on the defects of CdS for efficient photocatalytic H2 evolution under visible light irradiation. Chem Eng J, 2019, 370: 305–313
Liang G, Waqas M, Yang B, et al. Enhanced photocatalytic hydrogen evolution under visible light irradiation by p-type MoS2/n-type Ni2P doped g-C3N4. Appl Surf Sci, 2020, 504: 144448
Li Y, Wang L, Cai T, et al. Glucose-assisted synthesize 1D/2D nearly vertical CdS/MoS2 heterostructures for efficient photocatalytic hydrogen evolution. Chem Eng J, 2017, 321: 366–374
Reddy DA, Park H, Ma R, et al. Heterostructured WS2-MoS2 ultrathin nanosheets integrated on CdS nanorods to promote charge separation and migration and improve solar-driven photocatalytic hydrogen evolution. ChemSusChem, 2017, 10: 1563–1570
Zheng W, Feng W, Zhang X, et al. Anisotropic growth of nonlayered CdS on MoS2 monolayer for functional vertical heterostructures. Adv Funct Mater, 2016, 26: 2648–2654
Niu X, Bai X, Zhou Z, et al. Rational design and characterization of direct Z-scheme photocatalyst for overall water splitting from excited state dynamics simulations. ACS Catal, 2020, 10: 1976–1983
Zhang L, Zhang H, Jiang C, et al. Z-scheme system of WO3@MoS2/CdS for photocatalytic evolution H2:MoS2 as the charge transfer mode switcher, electron-hole mediator and cocatalyst. Appl Catal B-Environ, 2019, 259: 118073
Zhao H, Yang X, Xu R, et al. CdS/NH2-UiO-66 hybrid membrane reactors for the efficient photocatalytic conversion of CO2. J Mater Chem A, 2018, 6: 20152–20160
Wang H, Naghadeh SB, Li C, et al. Enhanced photoelectrochemical and photocatalytic activities of CdS nanowires by surface modification with MoS2 nanosheets. Sci China Mater, 2018, 61: 839–850
Hao H, Zhang L, Wang W, et al. Photocatalytic hydrogen evolution coupled with efficient selective benzaldehyde production from benzyl alcohol aqueous solution over ZnS-NixSy, composites. ACS Sustain Chem Eng, 2019, 7: 10501–10508
Chai Z, Zeng TT, Li Q, 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, 2016, 138: 10128–10131
Li F, Wang Y, Du J, et al. Simultaneous oxidation of alcohols and hydrogen evolution in a hybrid system under visible light irradiation. Appl Catal B-Environ, 2018, 225: 258–263
Zhang L, Jiang D, Irfan RM, et al. Highly efficient and selective photocatalytic dehydrogenation of benzyl alcohol for simultaneous hydrogen and benzaldehyde production over Ni-decorated Zn0.5Cd0.5S solid solution. J Energy Chem, 2019, 30: 71–77
Hong S, Kumar DP, Kim EH, et al. Earth abundant transition metal-doped few-layered MoS2 nanosheets on CdS nanorods for ultra-efficient photocatalytic hydrogen production. J Mater Chem A, 2017, 5: 20851–20859
Li LL, Yin XL, Pang DH, et al. One-pot synthesis of MoS2/CdS nanosphere heterostructures for efficient H2 evolution under visible light irradiation. Int J Hydrogen Energy, 2019, 44: 31930–31939
Reddy DA, Park H, Hong S, et al. Hydrazine-assisted formation of ultrathin MoS2 nanosheets for enhancing their co-catalytic activity in photocatalytic hydrogen evolution. J Mater Chem A, 2017, 5: 6981–6991
Xie J, Zhang J, Li S, et al. Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution. J Am Chem Soc, 2013, 135: 17881–17888
Yi JD, Shi PC, Liang J, et al. Porous hollow MoS2 microspheres derived from core-shell sulfonated polystyrene microspheres@MoS2 nanosheets for efficient electrocatalytic hydrogen evolution. Inorg Chem Front, 2017, 4: 741–747
Yan Z, Du L, Lee Phillips D. Multilayer core-shell MoS2/CdS nanorods with very high photocatalytic activity for hydrogen production under visible-light excitation and investigation of the photocatalytic mechanism by femtosecond transient absorption spectroscopy. RSC Adv, 2017, 7: 55993–55999
Yin XL, Li LL, Jiang WJ, et al. MoS2/CdS nanosheets-on-nanorod heterostructure for highly efficient photocatalytic H2 generation under visible light irradiation. ACS Appl Mater Interfaces, 2016, 8: 15258–15266
Hou Y, Laursen AB, Zhang J, et al. Layered nanojunctions for hydrogen-evolution catalysis. Angew Chem Int Ed, 2013, 52: 3621–3625
Kadam SR, Gosavi SW, Kale BB, et al. Unique CdS@MoS2 core shell heterostructure for efficient hydrogen generation under natural sunlight. Sci Rep, 2019, 9: 12036
Liu H, Cheng S, Wu M, et al. Photoelectrocatalytic degradation of sulfosalicylic acid and its electrochemical impedance spectroscopy investigation. J Phys Chem A, 2000, 104: 7016–7020
Zhao X, Xu T, Yao W, et al. Photoelectrocatalytic degradation of 4-chlorophenol at Bi2WO6 nanoflake film electrode under visible light irradiation. Appl Catal B-Environ, 2007, 72: 92–97
Zhao W, Li J, Dai B, et al. Simultaneous removal of tetracycline and Cr(VI) by a novel three-dimensional AgI/BiVO4 p-n junction photocatalyst and insight into the photocatalytic mechanism. Chem Eng J, 2019, 369: 716–725
Wu H, Meng S, Zhang J, et al. Construction of two-dimensionally relative p-n heterojunction for efficient photocatalytic redox reactions under visible light. Appl Surf Sci, 2020, 505: 144638
Lin R, Wan J, Xiong Y, et al. A quantitative study of charge carrier dynamics in well-defined WO3 nanowires and nanosheets: insight into the crystal facet effect in photocatalysis. J Am Chem Soc, 2018, 140: 9078–9082
Li J, Chen Y, Yang X, et al. Visible-light-mediated high-efficiency catalytic oxidation of sulfides using wrinkled C3N4 nanosheets. J Catal, 2020, 381: 579–589
Wu Z, Ouyang M, Wang D. Construction of WS2/MoSe2 heterojunction for efficient photoelectrocatalytic hydrogen evolution. Mater Sci Semicond Proc, 2020, 107: 104822
Chen C, Li M, Jia Y, et al. Surface defect-engineered silver silicate/ceria p-n heterojunctions with a flower-like structure for boosting visible light photocatalysis with mechanistic insight. J Colloid Interface Sci, 2020, 564: 442–453
Li H, Qin F, Yang Z, et al. New reaction pathway induced by plasmon for selective benzyl alcohol oxidation on BiOCl possessing oxygen vacancies. J Am Chem Soc, 2017, 139: 3513–3521
Sankar M, Nowicka E, Carter E, et al. The benzaldehyde oxidation paradox explained by the interception of peroxy radical by benzyl alcohol. Nat Commun, 2014, 5: 3332
Nouri M, Zare-Dehnavi N, Jamali-Sheini F, et al. Synthesis and characterization of type-II p(CuxSey)/n(g-C3N4) heterojunction with enhanced visible-light photocatalytic performance for degradation of dye pollutants. Colloids Surfs A-Physicochem Eng Aspects, 2020, 595: 124656
Wang Y, Zhang Z, Zhang L, et al. Visible-Light driven overall conversion of CO2 and H2O to CH4 and O2 on 3D-SiC@2D-MoS2 heterostructure. J Am Chem Soc, 2018, 140: 14595–14598
Xu G, Wang X, Sun Y, et al. Metallic and ferromagnetic MoS2 nanobelts with vertically aligned edges. Nano Res, 2015, 8: 2946–2953
Xiao X, Jiang J, Zhang L. Selective oxidation of benzyl alcohol into benzaldehyde over semiconductors under visible light: The case of Bi12O17Cl2 nanobelts. Appl Catal B-Environ, 2013, 142–143: 487–493
Yin XL, Liu J, Jiang WJ, et al. Urchin-like Au@CdS/WO3 micro/nano heterostructure as a visible-light driven photocatalyst for efficient hydrogen generation. Chem Commun, 2015, 51: 13842–13845
Zhao Q, Ji M, Qian H, et al. Controlling structural symmetry of a hybrid nanostructure and its effect on efficient photocatalytic hydrogen evolution. Adv Mater, 2014, 26: 1387–1392
Acknowledgements
This work was supported by the National Key Research and Development Program of China (2017YFA0700102), the National Natural Science Foundation of China (21520102001, 21871263 and 21671188), the Key Research Program of Frontier Sciences, CAS (QYZDJ-SSW-SLH045), and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000).
Author information
Authors and Affiliations
Contributions
Gao S and Li P designed and engineered the experiments; Li P performed the experiments and the characterizations; Zhao H designed the materials; Li P wrote the paper with support from Gao S and Cao R. All authors contributed to the general discussion.
Corresponding authors
Additional information
Conflict of interest
The authors declare that they have no conflict of interest.
Supplementary information
Experimental details and supporting data are available in the online version of the paper.
Peixian Li received his Bachelor’s degree from the School of Materials Science and Engineering, Liaocheng University in 2018. He is currently a Master candidate jointly trained by Fujian Normal University and Fujian Institute of Research on the Structure of Matter (FJIRSM).
Shuiying Gao received her Master degree from Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences (CAS) in 2002. She obtained her PhD from FJIRSM, CAS, in 2006. In 2014, she became a professor at FJIRSM. Her research interests focus on thin-film materials and photocatalysis.
Rong Cao was born in Fujian Province, China. He obtained his PhD from FJIRSM, CAS, in 1993. Following post-doctoral experience at the Hong Kong Polytechnic University and a Japan Society for the Promotion of Science (JSPS) Fellowship at Nagoya University, he became a professor at FJIRSM in 1998. He is currently the director of FJIRSM. His main research interests include supramolecular chemistry, inorganicorganic hybrid materials, and nanocatalysis.
Supporting Information
40843_2020_1448_MOESM1_ESM.pdf
Visible-light-driven photocatalytic hydrogen production coupled with selective oxidation of benzyl alcohol over CdS@MoS2 heterostructures
Rights and permissions
About this article
Cite this article
Li, P., Zhao, H., Yan, X. et al. Visible-light-driven photocatalytic hydrogen production coupled with selective oxidation of benzyl alcohol over CdS@MoS2 heterostructures. Sci. China Mater. 63, 2239–2250 (2020). https://doi.org/10.1007/s40843-020-1448-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1448-2