Simultaneously Efficient Solar Light Harvesting and Charge Transfer of Hollow Octahedral Cu2S/CdS p–n Heterostructures for Remarkable Photocatalytic Hydrogen Generation

Yanting Zhang1, Lei Ran1, Zhuwei Li1, Panlong Zhai1, Bo Zhang1, Zhixing Fan1, Chen Wang1, Xiaomeng Zhang1, Jungang Hou1, Licheng Sun2
1State Key Laboratory of Fine Chemicals & School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
2Center of Artificial Photosynthesis for Solar Fuels, School of Science, Westlake University, Hangzhou 310024, China

Tóm tắt

AbstractSolar-driven water splitting is a promising alternative to industrial hydrogen production. This study reports an elaborate design and synthesis of the integration of cadmium sulfide (CdS) quantum dots and cuprous sulfide (Cu2S) nanosheets as three-dimensional (3D) hollow octahedral Cu2S/CdS p–n heterostructured architectures by a versatile template and one-pot sulfidation strategy. 3D hierarchical hollow nanostructures can strengthen multiple reflections of solar light and provide a large specific surface area and abundant reaction sites for photocatalytic water splitting. Owing to the construction of the p–n heterostructure as an ideal catalytic model with highly matched band alignment at Cu2S/CdS interfaces, the emerging internal electric field can facilitate the space separation and transfer of photoexcited charges between CdS and Cu2S and also enhance charge dynamics and prolong charge lifetimes. Notably, the unique hollow Cu2S/CdS architectures deliver a largely enhanced visible-light-driven hydrogen generation rate of 4.76 mmol/(g·h), which is nearly 8.5 and 476 times larger than that of pristine CdS and Cu2S catalysts, respectively. This work not only paves the way for the rational design and fabrication of hollow photocatalysts but also clarifies the crucial role of unique heterostructure in photocatalysis for solar energy conversion.

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Tài liệu tham khảo

Munir AB, Muhammad-Sukki F, Bani NA (2016) Renewables: solar energy needs focus. Nature 529(7587):466

Wu H, Tan HL, Toe CY et al (2020) Photocatalytic and photoelectrochemical systems: similarities and differences. Adv Mater 32(18):e1904717

Zhang XM, Liang HC, Li HZ et al (2020) Sequential chemistry toward core-shell structured metal sulfides as stable and highly efficient visible-light photocatalysts. Angewandte Chemie Int Ed 59(8):3287–3293

Wang PF, Shen ZR, Xia YG et al (2019) Atomic insights for optimum and excess doping in photocatalysis: a case study of few-layer Cu-ZnIn2S4. Adv Funct Mater 29(3):1807013

Gao HW, Liu C, Jeong HE et al (2012) Plasmon-enhanced photocatalytic activity of iron oxide on gold nanopillars. ACS Nano 6(1):234–240

Hou JG, Yang C, Cheng HJ et al (2014) High-performance p-Cu2O/n-TaON heterojunction nanorod photoanodes passivated with an ultrathin carbon sheath for photoelectrochemical water splitting. Energy Environ Sci 7(11):3758–3768

Hou JG, Cheng HJ, Zhu HM et al (2015) Three-dimensional bimetal graphene semiconductor coaxial nanowire arrays to harness charge flow for the photochemical reduction of carbon dioxide. Angew Chem Int Ed 127(29):8600–8604

Guo MJ, Zhao TY, Xing ZP et al (2020) Hollow octahedral Cu2-xS/CdS/Bi2S3 p-n-p type tandem heterojunctions for efficient photothermal effect and robust visible-light-driven photocatalytic performance. ACS Appl Mater Interfaces 12(36):40328–40338

Huang Y, Fang YJ, Lu XF et al (2020) Co3O4 hollow nanoparticles embedded in mesoporous walls of carbon nanoboxes for efficient lithium storage. Angew Chem Int Ed 59(45):19914–19918

Zhang P, Luan DY, Lou XW et al (2020) Fabrication of CdS frame-in-cage particles for efficient photocatalytic hydrogen generation under visible-light irradiation. Adv Mater 32(39):2004561

Wang Y, Wang SB, Zhang SL et al (2020) Formation of hierarchical FeCoS2-CoS2 double-shelled nanotubes with enhanced performance for photocatalytic reduction of CO2. Angew Chem Int Ed 59(29):11918–11922

Wang SB, Guan BY, Lou XWD et al (2018) Construction of ZnIn2S4-In2O3 hierarchical tubular heterostructures for efficient CO2 photoreduction. J Am Chem Soc 140(15):5037–5040

Wang SB, Wang Y, Zhang SL et al (2019) Supporting ultrathin ZnIn2S4 nanosheets on Co/N-doped graphitic carbon nanocages for efficient photocatalytic H2 generation. Adv Mater 31(41):1903404

Wei YZ, Wan JW, Wang JY et al (2021) Hollow multishelled structured SrTiO3 with La/Rh Co-doping for enhanced photocatalytic water splitting under visible light. Small. https://doi.org/10.1002/smll.202005345

Jia TK, Liu M, Zheng CY et al (2020) One pot hydrothermal synthesis of La-doped ZnIn2S4 microspheres with improved visible-light photocatalytic performance. Nanomaterials. 10(10):2026

Shi JW, Chen F, Hou LL et al (2021) Eosin Y bidentately bridged on UiO-66-NH2 by solvothermal treatment towards enhanced visible-light-driven photocatalytic H2 production. Appl Catal B Environ 280:119385

Zhang SY, Du M, Xing ZP et al (2020) Defect-rich and electron-rich mesoporous Ti-MOFs based NH2-MIL-125(Ti)@ZnIn2S4/CdS hierarchical tandem heterojunctions with improved charge separation and enhanced solar-driven photocatalytic performance. Appl Catal B: Environ 262:118202

He YQ, Rao H, Song KP et al (2019) (2019) 3D hierarchical ZnIn2S4 nanosheets with rich Zn vacancies boosting photocatalytic CO2 reduction. Adv Funct Mater 29(45):1905153

Wang L, Zhou HH, Zhang HZ et al (2020) Facile in situ formation of a ternary 3D ZnIn2S4-MoS2 microsphere/1D CdS nanorod heterostructure for high efficiency visible-light photocatalytic H2 production. Nanoscale 12(25):13791–13800

Cao SY, Wu YZ, Hou JG et al (2020) 3D porous pyramid heterostructure array realizing efficient photo-electrochemical performance. Adv Energy Mater 10(5):1902935

Qiu BC, Zhu QH, Du MM et al (2017) Efficient solar light harvesting CdS/Co9S8 hollow cubes for Z-scheme photocatalytic water splitting. Angewandte Chemie Int Ed 56(10):2684–2688

Zhao XX, Feng JR, Liu J et al (2018) An efficient, visible-light-driven, hydrogen evolution catalyst NiS/ZnxCd1-xS nanocrystal derived from a metal–organic framework. Angewandte Chemie Int Ed 57(31):9790–9794

Zhang TX, Meng FL, Cheng Y et al (2021) Z-scheme transition metal bridge of Co9S8/Cd/CdS tubular heterostructure for enhanced photocatalytic hydrogen evolution. Appl Catal B: Environ 286:119853

Zhang J, Yu J, Zhang Y et al (2011) Visible light photocatalytic H2 production activity of CuS/ZnS porous nanosheets based on photoinduced interfacial charge transfer. Nano Lett 11(11):4774–4779

Sheng JL, Chen JH, Kang JH et al (2019) Octahedral Cu2O@Co(OH)2 nanocages with hierarchical flake-like walls and yolk-shell structures for enhanced electrocatalytic activity. ChemCatChem 11(10):2520–2525

Zheng DD, Zhang GG, Wang XC et al (2015) Integrating CdS quantum dots on hollow graphitic carbon nitride nanospheres for hydrogen evolution photocatalysis. Appl Catal B: Environ 179:479–488

Ji MW, Li XY, Wang HZ et al (2017) Versatile synthesis of yolk/shell hybrid nanocrystals via ion-exchange reactions for novel metal/semiconductor and semiconductor/semiconductor conformations. Nano Res 10(9):2977–2987

Ran L, Yin LW (2017) Double-walled heterostructured Cu2-xSe/Cu7S4 nanoboxes with enhanced electrocatalytic activity for quantum dot sensitized solar cells. CrystEngComm 19(37):5640–5652

Bhavani P, Kumar DP, Shim HS et al (2020) In situ addition of Ni salt onto a skeletal Cu7S4 integrated CdS nanorod photocatalyst for efficient production of H2 under solar light irradiation. Catal Sci Technol 1(11):3542–3551

Zhong LX, Mao BD, Liu M et al (2021) Construction of hierarchical photocatalysts by growing ZnIn2S4 nanosheets on Prussian blue analogue-derived bimetallic sulfides for solar co-production of H2 and organic chemicals. J Energy Chem 54:386–394

Tang R, Yin LW (2015) Enhanced photovoltaic performance of dye-sensitized solar cells based on Sr-doped TiO2/SrTiO3 nanorod array heterostructures. J Mater Chem A 3(33):17417–17425

Xu WW, Tian W, Meng LX et al (2021) Interfacial chemical bond-modulated Z-scheme charge transfer for efficient photoelectrochemical water splitting. Adv Energy Mater 11(8):2003500

Tan PF, Zhu AQ, Qiao LL et al (2019) Constructing a direct Z-scheme photocatalytic system based on 2D/2D WO3/ZnIn2S4 nanocomposite for efficient hydrogen evolution under visible light. Inorg Chem Front 6(4):929–939

Cai XY, Mao L, Yang SQ et al (2018) Ultrafast charge separation for full solar spectrum-activated photocatalytic H2 generation in a black phosphorus-Au-CdS heterostructure. ACS Energy Lett 3(4):932–939

Zhang SQ, Liu X, Liu CB et al (2018) MoS2 quantum dot growth induced by S vacancies in a ZnIn2S4 monolayer: atomic-level heterostructure for photocatalytic hydrogen production. ACS Nano 12(1):751–758

Swain G, Sultana S, Parida K et al (2019) One-pot-architectured Au- nanodot-promoted MoS2/ZnIn2S4: a novel p–n heterojunction photocatalyst for enhanced hydrogen production and phenol degradation. Inorg Chem 58(15):9941–9955

Chen YB, Li JF, Liao PY et al (2020) Cascaded electron transition in CuWO4/CdS/CDs heterostructure accelerating charge separation towards enhanced photocatalytic activity. Chin Chem Lett 31(6):1516–1519

Xiao R, Zhao CX, Zou ZY et al (2020) In situ fabrication of 1D CdS nanorod/2D Ti3C2 MXene nanosheet Schottky heterojunction toward enhanced photocatalytic hydrogen evolution. Appl Catal B: Environ 268:118382

Mao L, Cai XY, Zhu MS et al (2021) Hierarchically 1D CdS decorated on 2D perovskite-type La2Ti2O7 nanosheet hybrids with enhanced photocatalytic performance. Rare Met 40(5):1067–1076

Ding MY, Xiao R, Zhao CX et al (2020) Evidencing interfacial charge transfer in 2D CdS/2D MXene Schottky heterojunctions toward high-efficiency photocatalytic hydrogen production. Sol RRL 5(2):2000414

Cai L, Du YC, Guan XJ et al (2019) CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance. Chin Chem Lett 30(12):2363–2367

Zulfiqar S, Liu S, Rahman N et al (2021) Construction of S-scheme MnO2@CdS heterojunction with core-shell structure as H2-production photocatalyst. Rare Met. https://doi.org/10.1007/s12598-020-01616-w