Near-infrared absorbing 2D/3D ZnIn2S4/N-doped graphene photocatalyst for highly efficient CO2 capture and photocatalytic reduction

More info
  • ReceivedOct 18, 2019
  • AcceptedDec 18, 2019
  • PublishedJan 8, 2020


Funded by

the National Natural Science Foundation of China(51961135303,51932007,21871217,U1705251)

the National Key Research and Development Program(2018YFB1502001)

and the Innovative Research Funds of SKLWUT(2017-ZD-4)


This work was supported by the National Natural Science Foundation of China (51961135303, 51932007, 21871217 and U1705251), the National Key Research and Development Program of China (2018YFB1502001) and Innovative Research Funds of SKLWUT (2017-ZD-4).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Yu J, Liu G and Xia Y conceived and designed the experiments. Xia Y carried out the synthesis of the materials and photocatalytic test. Xia Y, Fan J and Cheng B performed the material characterizations. Xia Y, Yu J and Liu G contributed to data analysis. Yu J, Liu G and Cheng B supervised the project. Yu J, Liu G and Xia Y wrote the paper. All authors discussed the results and commented on the manuscript.

Author information

Yang Xia received his MS degree from South Central University for Nationalities in 2017. He is now a PhD candidate under the supervision of Prof. Jiaguo Yu at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology. His current research includes semiconductor photocatalysis, photocatalytic H2 production, and CO2 reduction.

Jiaguo Yu received his BS and MS degrees in chemistry from Central China Normal University and Xi’an Jiaotong University, respectively, and his PhD degree in materials science in 2000 from Wuhan University of Technology. In 2000, he became a Professor at Wuhan University of Technology. His current research interests include semiconductor photocatalysis, photocatalytic hydrogen production, CO2 reduction to hydrocarbon fuels, and so on.

Gang Liu received his PhD degree in 2000 from Texas A&M University, USA. Then he did his postdoctoral work at Brookhaven National Laboratory, University of Pennsylvania and Temple University. He joined the National Center for Nanoscience and Technology, China, in 2007 as an associate professor. His research interests lie in the characterization and properties of a variety of nanoscale materials important in environmental control and clean energy production.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Li X, Yu J, Jaroniec M, et al. Cocatalysts for selective photoreduction of CO2 into solar fuels. Chem Rev, 2019, 119: 3962-4179 CrossRef PubMed Google Scholar

[2] Ran J, Jaroniec M, Qiao SZ. Cocatalysts in semiconductor-based photocatalytic CO2 reduction: achievements, challenges, and opportunities. Adv Mater, 2018, 30: 1704649 CrossRef PubMed Google Scholar

[3] Han C, Li J, Ma Z, et al. Black phosphorus quantum dot/g-C3N4 composites for enhanced CO2 photoreduction to CO. Sci China Mater, 2018, 61: 1159-1166 CrossRef Google Scholar

[4] Low J, Dai B, Tong T, et al. In situ irradiated X-ray photoelectron spectroscopy investigation on a direct Z-scheme TiO2/CdS composite film photocatalyst. Adv Mater, 2019, 31: 1802981 CrossRef PubMed Google Scholar

[5] 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 CrossRef Google Scholar

[6] Di T, Xu Q, Ho WK, et al. Review on metal sulphide-based Z-scheme photocatalysts. ChemCatChem, 2019, 11: 1394-1411 CrossRef Google Scholar

[7] Zhang N, Long R, Gao C, et al. Recent progress on advanced design for photoelectrochemical reduction of CO2 to fuels. Sci China Mater, 2018, 61: 771-805 CrossRef Google Scholar

[8] Li P, Hou C, Zhang X, et al. Ethylenediamine-functionalized CdS/tetra(4-carboxyphenyl)porphyrin iron(III) chloride hybrid system for enhanced CO2 photoreduction. Appl Surf Sci, 2018, 459: 292-299 CrossRef Google Scholar

[9] Zhou M, Wang S, Yang P, et al. Layered heterostructures of ultrathin polymeric carbon nitride and ZnIn2S4 nanosheets for photocatalytic CO2 reduction. Chem Eur J, 2018, 24: 18529-18534 CrossRef PubMed Google Scholar

[10] Meng A, Zhang L, Cheng B, et al. TiO2–MnOx–Pt hybrid multiheterojunction film photocatalyst with enhanced photocatalytic CO2-reduction activity. ACS Appl Mater Interfaces, 2019, 11: 5581-5589 CrossRef Google Scholar

[11] Crake A, Christoforidis KC, Gregg A, et al. The effect of materials architecture in TiO2/MOF composites on CO2 photoreduction and charge transfer. Small, 2019, 15: 1805473 CrossRef PubMed Google Scholar

[12] Yu S, Wilson AJ, Heo J, et al. Plasmonic control of multi-electron transfer and C–C coupling in visible-light-driven CO2 reduction on Au nanoparticles. Nano Lett, 2018, 18: 2189-2194 CrossRef PubMed Google Scholar

[13] Zhou L, Xu YF, Chen BX, et al. Synthesis and photocatalytic application of stable lead-free Cs2AgBiBr6 perovskite nanocrystals. Small, 2018, 14: 1703762 CrossRef PubMed Google Scholar

[14] Low J, Zhang L, Zhu B, et al. TiO2 photonic crystals with localized surface photothermal effect and enhanced photocatalytic CO2 reduction activity. ACS Sustain Chem Eng, 2018, 6: 15653-15661 CrossRef Google Scholar

[15] Li X, Wen J, Low J, et al. Design and fabrication of semiconductor photocatalyst for photocatalytic reduction of CO2 to solar fuel. Sci China Mater, 2014, 57: 70-100 CrossRef Google Scholar

[16] Fu J, Zhu B, Jiang C, et al. Hierarchical porous O-doped g-C3N4 with enhanced photocatalytic CO2 reduction activity. Small, 2017, 13: 1603938 CrossRef PubMed Google Scholar

[17] Low J, Zhang L, Tong T, et al. TiO2/MXene Ti3C2 composite with excellent photocatalytic CO2 reduction activity. J Catal, 2018, 361: 255-266 CrossRef Google Scholar

[18] Di T, Zhang J, Cheng B, et al. Hierarchically nanostructured porous TiO2(B) with superior photocatalytic CO2 reduction activity. Sci China Chem, 2018, 61: 344-350 CrossRef Google Scholar

[19] Wang S, Xu M, Peng T, et al. Porous hypercrosslinked polymer-TiO2-graphene composite photocatalysts for visible-light-driven CO2 conversion. Nat Commun, 2019, 10: 676 CrossRef PubMed Google Scholar

[20] Pang R, Teramura K, Asakura H, et al. Highly selective photocatalytic conversion of CO2 by water over Ag-loaded SrNb2O6 nanorods. Appl Catal B-Environ, 2017, 218: 770-778 CrossRef Google Scholar

[21] Raziq F, Sun L, Wang Y, et al. Synthesis of large surface-area g-C3N4 comodified with MnOx and Au-TiO2 as efficient visible-light photocatalysts for fuel production. Adv Energy Mater, 2018, 8: 1701580 CrossRef Google Scholar

[22] Thanh Truc NT, Hanh NT, Nguyen MV, et al. Novel direct Z-scheme Cu2V2O7/g-C3N4 for visible light photocatalytic conversion of CO2 into valuable fuels. Appl Surf Sci, 2018, 457: 968-974 CrossRef Google Scholar

[23] Wang S, Guan BY, Lou XWD. Construction of ZnIn2S4–In2O3 hierarchical tubular heterostructures for efficient CO2 photoreduction. J Am Chem Soc, 2018, 140: 5037-5040 CrossRef PubMed Google Scholar

[24] Xu F, Zhu B, Cheng B, et al. 1D/2D TiO2/MoS2 hybrid nanostructures for enhanced photocatalytic CO2 reduction. Adv Opt Mater, 2018, 6: 1800911 CrossRef Google Scholar

[25] Li H, Gao Y, Zhou Y, et al. Construction and nanoscale detection of interfacial charge transfer of elegant Z-scheme WO3/Au/In2S3 nanowire arrays. Nano Lett, 2016, 16: 5547-5552 CrossRef PubMed Google Scholar

[26] She H, Zhou H, Li L, et al. Construction of a two-dimensional composite derived from TiO2 and SnS2 for enhanced photocatalytic reduction of CO2 into CH4. ACS Sustain Chem Eng, 2018, 7: 650-659 CrossRef Google Scholar

[27] Cho KM, Kim KH, Park K, et al. Amine-functionalized graphene/CdS composite for photocatalytic reduction of CO2. ACS Catal, 2017, 7: 7064-7069 CrossRef Google Scholar

[28] Zhu Z, Han Y, Chen C, et al. Reduced graphene oxide-cadmium sulfide nanorods decorated with silver nanoparticles for efficient photocatalytic reduction carbon dioxide under visible light. ChemCatChem, 2018, 10: 1627-1634 CrossRef Google Scholar

[29] Fu ZC, Xu RC, Moore JT, et al. Highly efficient photocatalytic system constructed from CoP/carbon nanotubes or graphene for visible-light-driven CO2 reduction. Chem Eur J, 2018, 24: 4273-4278 CrossRef PubMed Google Scholar

[30] Wang Y, Cai Q, Yao M, et al. Easy synthesis of ordered mesoporous carbon–carbon nanotube nanocomposite as a promising support for CO2 photoreduction. ACS Sustain Chem Eng, 2018, 6: 2529-2534 CrossRef Google Scholar

[31] Li M, Wang M, Zhu L, et al. Facile microwave assisted synthesis of N-rich carbon quantum dots/dual-phase TiO2 heterostructured nanocomposites with high activity in CO2 photoreduction. Appl Catal B-Environ, 2018, 231: 269-276 CrossRef Google Scholar

[32] Kulandaivalu T, Abdul Rashid S, Sabli N, et al. Visible light assisted photocatalytic reduction of CO2 to ethane using CQDs/Cu2O nanocomposite photocatalyst. Diamond Related Mater, 2019, 91: 64-73 CrossRef Google Scholar

[33] Ye S, Feng J, Wu P. Deposition of three-dimensional graphene aerogel on nickel foam as a binder-free supercapacitor electrode. ACS Appl Mater Interfaces, 2013, 5: 7122-7129 CrossRef PubMed Google Scholar

[34] Ren L, Hui KS, Hui KN. Self-assembled free-standing three-dimensional nickel nanoparticle/graphene aerogel for direct ethanol fuel cells. J Mater Chem A, 2013, 1: 5689 CrossRef Google Scholar

[35] Chen Z, Li H, Tian R, et al. Three dimensional graphene aerogels as binder-less, freestanding, elastic and high-performance electrodes for lithium-ion batteries. Sci Rep, 2016, 6: 27365 CrossRef PubMed Google Scholar

[36] He K, Chen G, Zeng G, et al. Three-dimensional graphene supported catalysts for organic dyes degradation. Appl Catal B-Environ, 2018, 228: 19-28 CrossRef Google Scholar

[37] Fan Y, Ma W, Han D, et al. Convenient recycling of 3D AgX/graphene aerogels (X = Br, Cl) for efficient photocatalytic degradation of water pollutants. Adv Mater, 2015, 27: 3767-3773 CrossRef PubMed Google Scholar

[38] Wan W, Lin Y, Prakash A, et al. Three-dimensional carbon-based architectures for oil remediation: from synthesis and modification to functionalization. J Mater Chem A, 2016, 4: 18687-18705 CrossRef Google Scholar

[39] Hasani A, Sharifi Dehsari H, Amiri Zarandi A, et al. Visible light-assisted photoreduction of graphene oxide using CdS nanoparticles and gas sensing properties. J Nanomaterials, 2015, 2015: 1-11 CrossRef Google Scholar

[40] Li L, He S, Liu M, et al. Three-dimensional mesoporous graphene aerogel-supported SnO2 nanocrystals for high-performance NO2 gas sensing at low temperature. Anal Chem, 2015, 87: 1638-1645 CrossRef PubMed Google Scholar

[41] Song Z, Wei Z, Wang B, et al. Sensitive room-temperature H2S gas sensors employing SnO2 quantum wire/reduced graphene oxide nanocomposites. Chem Mater, 2016, 28: 1205-1212 CrossRef Google Scholar

[42] Xia Y, Cui W, Zhang H, et al. Synthesis of three-dimensional graphene aerogel encapsulated n-octadecane for enhancing phase-change behavior and thermal conductivity. J Mater Chem A, 2017, 5: 15191-15199 CrossRef Google Scholar

[43] Han W, Zang C, Huang Z, et al. Enhanced photocatalytic activities of three-dimensional graphene-based aerogel embedding TiO2 nanoparticles and loading MoS2 nanosheets as co-catalyst. Int J Hydrogen Energy, 2014, 39: 19502-19512 CrossRef Google Scholar

[44] Tong Z, Yang D, Shi J, et al. Three-dimensional porous aerogel constructed by g-C3N4 and graphene oxide nanosheets with excellent visible-light photocatalytic performance. ACS Appl Mater Interfaces, 2015, 7: 25693-25701 CrossRef Google Scholar

[45] Song X, Lin L, Rong M, et al. Mussel-inspired, ultralight, multifunctional 3D nitrogen-doped graphene aerogel. Carbon, 2014, 80: 174-182 CrossRef Google Scholar

[46] Zhao Y, Xie X, Zhang J, et al. MoS2 nanosheets supported on 3D graphene aerogel as a highly efficient catalyst for hydrogen evolution. Chem Eur J, 2015, 21: 15908-15913 CrossRef PubMed Google Scholar

[47] Ding Y, Gao Y, Li Z. Carbon quantum dots (CQDs) and Co(dmgH)2PyCl synergistically promote photocatalytic hydrogen evolution over hexagonal ZnIn2S4. Appl Surf Sci, 2018, 462: 255-262 CrossRef Google Scholar

[48] Ma J, Wang M, Lei G, et al. Polyaniline derived N-doped carbon-coated cobalt phosphide nanoparticles deposited on N-doped graphene as an efficient electrocatalyst for hydrogen evolution reaction. Small, 2018, 14: 1702895 CrossRef PubMed Google Scholar

[49] Liu B, Ren X, Chen L, et al. High efficient adsorption and storage of iodine on S, N co-doped graphene aerogel. J Hazard Mater, 2019, 373: 705-715 CrossRef PubMed Google Scholar

[50] Duan J, Chen S, Dai S, et al. Shape control of Mn3O4 nanoparticles on nitrogen-doped graphene for enhanced oxygen reduction activity. Adv Funct Mater, 2014, 24: 2072-2078 CrossRef Google Scholar

[51] Zhao X, Wang Z, Xie Y, et al. Photocatalytic reduction of graphene oxide-TiO2 nanocomposites for improving resistive-switching memory behaviors. Small, 2018, 14: 1801325 CrossRef PubMed Google Scholar

[52] Xia Y, Li Q, Lv K, et al. Heterojunction construction between TiO2 hollowsphere and ZnIn2S4 flower for photocatalysis application. Appl Surf Sci, 2017, 398: 81-88 CrossRef Google Scholar

[53] Ye H, Wang H, Zhang B, et al. Tremella-like ZnIn2S4/graphene composite based photoelectrochemical sensor for sensitive detection of dopamine. Talanta, 2018, 186: 459-466 CrossRef PubMed Google Scholar

[54] Kale SB, Kalubarme RS, Mahadadalkar MA, et al. Hierarchical 3D ZnIn2S4/graphene nano-heterostructures: their in situ fabrication with dual functionality in solar hydrogen production and as anodes for lithium ion batteries. Phys Chem Chem Phys, 2015, 17: 31850-31861 CrossRef PubMed Google Scholar

[55] Zou H, He B, Kuang P, et al. NixSy nanowalls/nitrogen-doped graphene foam is an efficient trifunctional catalyst for unassisted artificial photosynthesis. Adv Funct Mater, 2018, 28: 1706917 CrossRef Google Scholar

[56] Xu D, Cheng B, Wang W, et al. Ag2CrO4/g-C3N4/graphene oxide ternary nanocomposite Z-scheme photocatalyst with enhanced CO2 reduction activity. Appl Catal B-Environ, 2018, 231: 368-380 CrossRef Google Scholar

[57] Bin Z, Hui L. Three-dimensional porous graphene-Co3O4 nanocomposites for high performance photocatalysts. Appl Surf Sci, 2015, 357: 439-444 CrossRef Google Scholar

[58] Jia L, Wang DH, Huang YX, et al. Highly durable N-doped graphene/CdS nanocomposites with enhanced photocatalytic hydrogen evolution from water under visible light irradiation. J Phys Chem C, 2011, 115: 11466-11473 CrossRef Google Scholar

[59] Chen D, Huang S, Huang R, et al. Electron beam-induced microstructural evolution of SnS2 quantum dots assembled on N-doped graphene nanosheets with enhanced photocatalytic activity. Adv Mater Interfaces, 2019, 6: 1801759 CrossRef Google Scholar

[60] Qin W, Han L, Bi H, et al. Hydrogen storage in a chemical bond stabilized Co9S8–graphene layered structure. Nanoscale, 2015, 7: 20180-20187 CrossRef PubMed Google Scholar

[61] Song Y, Bai S, Zhu L, et al. Tuning pseudocapacitance via C–S bonding in WS2 nanorods anchored on N,S codoped graphene for high-power lithium batteries. ACS Appl Mater Interfaces, 2018, 10: 13606-13613 CrossRef Google Scholar

[62] Wei D, Liu Y, Wang Y, et al. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett, 2009, 9: 1752-1758 CrossRef PubMed Google Scholar

[63] Liu X, Dong G, Li S, et al. Direct observation of charge separation on anatase TiO2 crystals with selectively etched {001} facets. J Am Chem Soc, 2016, 138: 2917-2920 CrossRef PubMed Google Scholar

[64] Xu F, Meng K, Cheng B, et al. Enhanced photocatalytic activity and selectivity for CO2 reduction over a TiO2 nanofibre mat using Ag and MgO as Bi-cocatalyst. ChemCatChem, 2019, 11: 465-472 CrossRef Google Scholar

[65] Luo C, Zhao J, Li Y, et al. Photocatalytic CO2 reduction over SrTiO3: Correlation between surface structure and activity. Appl Surf Sci, 2018, 447: 627-635 CrossRef Google Scholar

[66] Zhou S, Shang L, Zhao Y, et al. Pd single-atom catalysts on nitrogen-doped graphene for the highly selective photothermal hydrogenation of acetylene to ethylene. Adv Mater, 2019, 31: 1900509 CrossRef PubMed Google Scholar

[67] Choi HS, Jeon HJ, Choi JH, et al. Tailoring open metal sites for selective capture of CO2 in isostructural metalloporphyrin porous organic networks. Nanoscale, 2015, 7: 18923-18927 CrossRef PubMed Google Scholar

[68] Zhao Z, Li Z, Lin YS. Adsorption and diffusion of carbon dioxide on metal−organic framework (MOF-5). Ind Eng Chem Res, 2009, 48: 10015-10020 CrossRef Google Scholar

[69] Wang J, Senkovska I, Oschatz M, et al. Imine-linked polymer-derived nitrogen-doped microporous carbons with excellent CO2 capture properties. ACS Appl Mater Interfaces, 2013, 5: 3160-3167 CrossRef PubMed Google Scholar

[70] An L, Liu S, Wang L, et al. Novel nitrogen-doped porous carbons derived from graphene for effective CO2 capture. Ind Eng Chem Res, 2019, 58: 3349-3358 CrossRef Google Scholar

[71] Chen J, Yang J, Hu G, et al. Enhanced CO2 capture capacity of nitrogen-doped biomass-derived porous carbons. ACS Sustain Chem Eng, 2016, 4: 1439-1445 CrossRef Google Scholar

[72] Chandra V, Yu SU, Kim SH, et al. Highly selective CO2 capture on N-doped carbon produced by chemical activation of polypyrrole functionalized graphene sheets. Chem Commun, 2012, 48: 735-737 CrossRef PubMed Google Scholar

[73] Di T, Zhu B, Cheng B, et al. A direct Z-scheme g-C3N4/SnS2 photocatalyst with superior visible-light CO2 reduction performance. J Catal, 2017, 352: 532-541 CrossRef Google Scholar

[74] Meng A, Wu S, Cheng B, et al. Hierarchical TiO2/Ni(OH)2 composite fibers with enhanced photocatalytic CO2 reduction performance. J Mater Chem A, 2018, 6: 4729-4736 CrossRef Google Scholar

[75] Xu F, Zhang J, Zhu B, et al. CuInS2 sensitized TiO2 hybrid nanofibers for improved photocatalytic CO2 reduction. Appl Catal B-Environ, 2018, 230: 194-202 CrossRef Google Scholar

[76] Liu J, Fang W, Wei Z, et al. Efficient photocatalytic hydrogen evolution on N-deficient g-C3N4 achieved by a molten salt post-treatment approach. Appl Catal B-Environ, 2018, 238: 465-470 CrossRef Google Scholar

[77] Jurca B, Bucur C, Primo A, et al. N-doped defective graphene from biomass as catalyst for CO2 hydrogenation to methane. ChemCatChem, 2018, 3: cctc.201801984 CrossRef Google Scholar

  • Figure 1

    Typical FESEM images of (a) NGF and (b) ZIS/NGF. Insets: the high-magnification FESEM images. (c) TEM and (d) HRTEM images of ZIS/NGF. (e) STEM image of ZIS/NGF and (f–k) the corresponding elemental mapping images of Zn, In, S, C, N, and O.

  • Scheme 1

    Schematic illustration for the formation process of hierarchical 2D/3D ZnIn2S4/NGF composite.

  • Figure 2

    (a) XRD patterns of ZIS, NGF and ZIS/NGF samples. (b) FT-IR spectra of ZIS, GO, NGF and ZIS/NGF1 samples.

  • Figure 3

    (a) XPS survey spectra of ZIS, NGF, and ZIS/NGF1. High-resolution XPS spectra for (b) C 1s and (c) N 1s of NGF and ZIS/NGF1 either in dark or under 365 nm LED irradiation (denoted UV-ZIS/NGF1). High-resolution XPS spectra of (d) Zn 2p, (e) In 3d, and (f) S 2p core-levels of ZIS and ZIS/NGF1 either in dark or under 365 nm LED irradiation (denoted as UV-ZIS/NGF1).

  • Figure 4

    (a) N2 adsorption-desorption isotherms and pore-size distributions (inset) of ZIS, ZIS/GO1, and ZIS/NGF1. (b) UV-vis-NIR diffusive reflectance spectra of the as-prepared photocatalysts and the corresponding plots (inset) of transformed Kubelka-Munk function vs. photon energy of ZIS and ZIS/NGF1. CO2 adsorption isotherms for ZIS, ZIS/GO1 and ZIS/NGF1 at (c) 273 K and (d) 298 K. (e) The corresponding isosteric heats of CO2 adsorption on ZIS, ZIS/GO1 and ZIS/NGF1 calculated from the adsorption isotherms at 273 and 298 K. (f) Adsorption isotherms of CO2 and N2 on CNNA/rGO at 273 K and 1 atm.

  • Figure 5

    (a) Comparison of different samples in CO2 photoreduction into CH4, CO and CH3OH under simulated sunlight irradiation. (b, c) Reaction products on ZIS/NGF1 analyzed by GC-MS under 300 W Xe lamp irradiation for 1 h with 12CO2 and 13CO2 as a respective carbon source. (d) In-situ DRIFTS spectra of photocatalytic CO2 reduction by ZIS/NGF1 in dark and under LED light irradiation, respectively.

  • Figure 6

    (a) Nyquist plots of EIS. (b) Photoelectrode transient photocurrent response. (c) Time-resolved transient PL decay spectra. (d) Steady-state PL spectra of the ZIS, ZIS/GO1 and ZIS/NGF1 photocatalysts.

  • Figure 7

    (a) The XPS VB spectra of ZIS and ZIS/NGF1. (b) Mott-Schottky plots of ZIS and ZIS/NGF1 at a frequency of 1000 Hz in 0.5 mol L−1 Na2SO4. (c) Energy level diagram and the photogenerated charge carrier transfer process of NGF and ZIS before and after coupling under simulated sunlight irradiation.