Skip to main content Accessibility help

Bimetallic metal–organic frameworks-derived mesoporous CdxZn1−xS polyhedrons for enhanced photocatalytic hydrogen evolution

  • Feihu Mu (a1), Shijian Zhou (a2), Yun Wang (a2), Jian Wang (a2) and Yan Kong (a2)...


A bimetallic metal–organic frameworks (MOFs)-templated strategy was developed to fabricate mesoporous CdxZn1−xS polyhedrons with improved photocatalytic hydrogen evolution activity, and the formation mechanism of these mesoporous polyhedrons was discussed in detail. Incorporating Cd atoms, the Brunauer–Emmett–Teller surface areas of mesoporous CdxZn1−xS polyhedrons were significantly increased (271 m2/g), providing more exposed active sites compared with ZnS. In addition, suitable conduction band potential (< −0.55 eV) of the mesoporous CdxZn1−xS polyhedrons was also beneficial for the photocatalysis. Impressively, by the co-effects of mesoporous structure and modified conduction band, the mesoporous CdxZn1−xS polyhedrons exhibited better photocatalytic activity for hydrogen evolution than most reported photocatalysts without noble metals. The maximum hydrogen evolution rate of the CSZ3 reached 4.10 mmol/(h g) under visible-light irradiation and without any cocatalyst condition. This facile strategy for the construction of mesoporous CdxZn1−xS polyhedrons provided a deep insight to fabricate other metal sulfides for a variety of photochemical applications.


Corresponding author

a)Address all correspondence to this author. e-mail:


Hide All
1.Huang, Y. and Zhang, B.: Active cocatalysts for photocatalytic hydrogen evolution derived from nickel or cobalt amine complexes. Angew. Chem., Int. Ed. 56, 14804 (2017).
2.Chen, X., Shen, S., Guo, L., and Mao, S.S.: Semiconductor-based photocatalytic hydrogen generation. Chem. Rev. 110, 6503 (2010).
3.Wang, X., Jing, D., and Ni, M.: Solar photocatalytic energy conversion. Sci. Bull. 62, 597 (2017).
4.Shi, R., Cao, Y., Bao, Y., Zhao, Y., Waterhouse, G.I.N., Fang, Z., Wu, L-Z., Tung, C-H., Yin, Y., and Zhang, T.: Self-assembled Au/CdSe nanocrystal clusters for plasmon-mediated photocatalytic hydrogen evolution. Adv. Mater. 29, 1700803 (2017).
5.Fujishima, A. and Honda, K.: Electrochemical photolysis of water at a semiconductor electrode. nature 238, 37 (1972).
6.Schultz, D.M. and Yoon, T.P.: Solar synthesis: Prospects in visible light photocatalysis. Science 343, 1239176 (2014).
7.Song, Y., Li, J., and Wang, C.: Modification of porphyrin/dipyridine metal complexes on the surface of TiO2 nanotubes with enhanced photocatalytic activity for photoreduction of CO2 into methanol. J. Mater. Res. 33, 2612 (2018).
8.Han, C., Chen, Z., Zhang, N., Colmenares, J.C., and Xu, Y-J.: Hierarchically CdS decorated 1D ZnO nanorods-2D graphene hybrids: Low temperature synthesis and enhanced photocatalytic performance. Adv. Funct. Mater. 25, 221 (2015).
9.Zhou, C., Shi, R., Shang, L., Zhao, Y., Waterhouse, G.I.N., Wu, L-Z., Tung, C-H., and Zhang, T.: A sustainable strategy for the synthesis of pyrochlore H4Nb2O7 hollow microspheres as photocatalysts for overall water splitting. ChemPlusChem 82, 181 (2017).
10.Zhu, C., Liu, C., Zhou, Y., Fu, Y., Guo, S., Li, H., Zhao, S., Huang, H., Liu, Y., and Kang, Z.: Carbon dots enhance the stability of CdS for visible-light-driven overall water splitting. Appl. Catal., B 216, 114 (2017).
11.Li, Q., Li, X., Wageh, S., Al-Ghamdi, A.A., and Yu, J.: CdS/Graphene nanocomposite photocatalysts. Adv. Energy Mater. 5, 1500010 (2015).
12.Shang, L., Tong, B., Yu, H., Waterhouse, G.I.N., Zhou, C., Zhao, Y., Tahir, M., Wu, L-Z., Tung, C-H., and Zhang, T.: CdS nanoparticle-decorated Cd nanosheets for efficient visible light-driven photocatalytic hydrogen evolution. Adv. Energy Mater. 6, 1501241 (2016).
13.Liu, S., Chen, J., Xu, D., Zhang, X., and Shen, M.: Enhanced photocatalytic activity of direct Z-scheme Bi2O3/g-C3N4 composites via facile one-step fabrication. J. Mater. Res. 33, 1391 (2018).
14.Giannakoudakis, D.A., Travlou, N.A., Secor, J., and Bandosz, T.J.: Oxidized g-C3N4 nanospheres as catalytically photoactive linkers in MOF/g-C3N4 composite of hierarchical pore structure. Small 13, 1601758 (2017).
15.Pan, C., Takata, T., Nakabayashi, M., Matsumoto, T., Shibata, N., Ikuhara, Y., and Domen, K.: A complex perovskite-type oxynitride: The first photocatalyst for water splitting operable at up to 600 nm. Angew. Chem., Int. Ed. 54, 2955 (2015).
16.Chen, S., Takata, T., and Domen, K.: Particulate photocatalysts for overall water splitting. Nat. Rev. Mater. 2, 17050 (2017).
17.Zhang, S., Liu, X., Liu, C., Luo, S., Wang, L., Cai, T., Zeng, Y., Yuan, J., Dong, W., Pei, Y., and Liu, Y.: MoS2 quantum dot growth induced by S vacancies in a ZnIn2S4 monolayer: Atomic-level heterostructure for photocatalytic hydrogen production. ACS Nano 12, 751 (2018).
18.Li, Q. and Lian, T.: Exciton dissociation dynamics and light-driven H2 generation in colloidal 2D cadmium chalcogenide nanoplatelet heterostructures. Nano Res. 11, 3031 (2018).
19.Coughlan, C., Ibanez, M., Dobrozhan, O., Singh, A., Cabot, A., and Ryan, K.M.: Compound copper chalcogenide nanocrystals. Chem. Rev. 117, 5865 (2017).
20.Zhao, H., Ding, X., Zhang, B., Li, Y., and Wang, C.: Enhanced photocatalytic hydrogen evolution along with byproducts suppressing over Z-scheme CdxZn1−xS/Au/g-C3N4 photocatalysts under visible light. Sci. Bull. 62, 602 (2017).
21.Gaikwad, A.P., Tyagi, D., Betty, C.A., and Sasikala, R.: Photocatalytic and photo electrochemical properties of cadmium zinc sulfide solid solution in the presence of Pt and RuS2 dual co-catalysts. Appl. Catal., A 517, 91 (2016).
22.Sasikala, R., Shirole, A.R., Sudarsan, V., G. Jagannath, , Sudakar, C., Naik, R., Rao, R., and Bharadwaj, S.R.: Enhanced photocatalytic activity of indium and nitrogen co-doped TiO2–Pd nanocomposites for hydrogen generation. Appl. Catal., A 377, 47 (2010).
23.Gong, B., Lu, Y., Wu, P., Huang, Z., Zhu, Y., Dang, Z., Zhu, N., Lu, G., and Huang, J.: Enhanced photocatalytic activity over Cd0.5Zn0.5S with stacking fault structure combined with Cu2+ modified carbon nanotubes. Appl. Surf. Sci. 365, 280 (2016).
24.Kyne, F., Maguire, S., Obroin, S., Mcging, P., Mccann, S., and Wright, E.: Photocatalytic H2 evolution under visible light irradiation on Ni-doped ZnS photocatalyst. Chem. Commun. 182, 620 (2000).
25.Fang, Z., Liu, L., Wang, J., and Zhong, X.: Depositing a ZnxCd1−xS shell around CdSe core nanocrystals via a noninjection approach in aqueous media. J. Phys. Chem. C 113, 4301 (2009).
26.Fang, X., Zhai, T., Gautam, U.K., Li, L., Wu, L., Bando, Y., and Golberg, D.: ZnS nanostructures: From synthesis to applications. Prog. Mater. Sci. 56, 175 (2011).
27.Jiang, D.C., Sun, Z., Jia, H., Lu, D., and Du, P.: Cocatalyst-free CdS nanorods/ZnS nanoparticles composite for high-performance visible-light-driven hydrogen production from water. J. Mater. Chem. A 4, 675 (2015).
28.Shu, D., Wang, H., Wang, Y., Li, Y., Liu, X., Chen, X., Peng, X., Wang, X., Ruterana, P., and Wang, H.: Composition dependent activity of Fe1−xPtx decorated ZnCdS nanocrystals for photocatalytic hydrogen evolution. Int. J. Hydrogen Energy 42, 20888 (2017).
29.Levchuk, I., Würth, C., Krause, F., Osvet, A., Batentschuk, M., Resch-Genger, U., Kolbeck, C., Herre, P., Steinrück, H.P., Peukert, W., and Brabec, C.J.: Industrially scalable and cost-effective Mn2+ doped ZnxCd1−xS/ZnS nanocrystals with 70% photoluminescence quantum yield, as efficient down-shifting materials in photovoltaics. Energy Environ. Sci. 9, 1083 (2016).
30.An, C., Feng, J., Liu, J., Wei, G., Du, J., Wang, H., Jin, S., and Zhang, J.: NiS nanoparticle decorated MoS2 nanosheets as efficient promoters for enhanced solar H2 evolution over ZnxCd1−xS nanorods. Inorg. Chem. Front. 4, 1042 (2017).
31.Han, Z., Chen, G., Li, C., Yu, Y., and Zhou, Y.: Preparation of 1D cubic Cd0.8Zn0.2S solid-solution nanowires using levelling effect of TGA and improved photocatalytic H2-production activity. J. Mater. Chem. A 3, 1696 (2014).
32.Mei, Z., Zhang, M., Schneider, J., Wang, W., Zhang, N., Su, Y., Chen, B., Wang, S., Rogach, A.L., and Pan, F.: Hexagonal Zn1−xCdxS (0.2 ≤ x ≤ 1) solid solution photocatalysts for H2 generation from water. Catal. Sci. Technol. 7, 982 (2017).
33.Su, Y., Zhang, Z., Liu, H., and Wang, Y.: Cd0.2Zn0.8S@UiO-66-NH2 nanocomposites as efficient and stable visible-light-driven photocatalyst for H2 evolution and CO2 reduction. Appl. Catal., B 200, 448 (2017).
34.Xing, C., Zhang, Y., Yan, W., and Guo, L.: Band structure-controlled solid solution of Cd1−xCd1−xZnxSZnxS photocatalyst for hydrogen production by water splitting. Int. J. Hydrogen Energy 31, 2018 (2006).
35.Chen, J., Chen, J., and Li, Y.: Hollow ZnCdS dodecahedral cages for highly efficient visible-light-driven hydrogen generation. J. Mater. Chem. A 5, 24116 (2017).
36.Zhu, Q.L. and Xu, Q.: Metal–organic framework composites. Chem. Soc. Rev. 43, 5468 (2014).
37.Tian, P., He, X., Li, W., Zhao, L., Fang, W., Chen, H., Zhang, F., Zhang, W., and Wang, W.: Zr-MOFs based on Keggin-type polyoxometalates for photocatalytic hydrogen production. J. Mater. Sci. 53, 12016 (2018).
38.Liu, J., Zheng, J., Barpaga, D., Sabale, S., Arey, B., Derewinski, M.A., McGrail, B.P., and Motkuri, R.K.: A tunable bimetallic MOF-74 for adsorption chiller applications. Eur. J. Inorg. Chem. 2018, 885 (2018).
39.Fang, G., Zhou, J., Cai, Y., Liu, S., Tan, X., Pan, A., and Liang, S.: Metal–organic framework-templated two-dimensional hybrid bimetallic metal oxides with enhanced lithium/sodium storage capability. J. Mater. Chem. A 5, 13983 (2017).
40.Yu, Z., Bai, Y., Liu, Y., Zhang, S., Chen, D., Zhang, N., and Sun, K.: Metal–organic-framework-derived yolk–shell-structured cobalt-based bimetallic oxide polyhedron with high activity for electrocatalytic oxygen evolution. ACS Appl. Mater. Interfaces 9, 31777 (2017).
41.Zhang, P., Guan, B.Y., Yu, L., and Lou, X.W.D.: Formation of double-shelled zinc–cobalt sulfide dodecahedral cages from bimetallic zeolitic imidazolate frameworks for hybrid supercapacitors. Angew. Chem., Int. Ed. 56, 7141 (2017).
42.Huang, Z.F., Song, J., Li, K., Tahir, M., Wang, Y.T., Pan, L., Wang, L., Zhang, X., and Zou, J.J.: Hollow cobalt-based bimetallic sulfide polyhedra for efficient all-pH-value electrochemical and photocatalytic hydrogen evolution. J. Am. Chem. Soc. 138, 1359 (2016).
43.Qian, J., Li, T.T., Hu, Y., and Huang, S.: A bimetallic carbide derived from a MOF precursor for increasing electrocatalytic oxygen evolution activity. Chem. Commun. 53, 13027 (2017).
44.Huang, M., Mi, K., Zhang, J., Yu, H., Yu, T., Yuan, A., Kong, Q., and Xiong, S.: MOFs-derived Bi-metal embedded N-doped carbon polyhedral nanocages with enhanced lithium storage. J. Mater. Chem. A 5, 266 (2017).
45.Song, F.Z., Zhu, Q.L., Yang, X., Zhan, W.W., Pachfule, P., Tsumori, N., and Xu, Q.: Metal–organic framework templated porous carbon‐metal oxide/reduced graphene oxide as superior support of bimetallic nanoparticles for efficient hydrogen generation from formic acid. Adv. Energy Mater. 8, 1701416 (2017).
46.Liu, J., Li, R., Wang, Y., Wang, Y., Zhang, X., and Fan, C.: The active roles of ZIF-8 on the enhanced visible photocatalytic activity of Ag/AgCl: Generation of superoxide radical and adsorption. J. Alloys Compd. 693, 543 (2017).
47.Yan, C., Fan, Y.Z., Chen, L., Pan, M., Zhang, L.Y., Jiang, J.J., and Su, C.Y.: Time controlled structural/packing transformation and tunable luminescence of Cd(II)-chloride-triBZ-ntb coordination assemblies: An experimental and theoretical exploration. CrystEngComm 17, 546 (2014).
48.Han, L., Yu, X.Y., and Lou, X.W.: formation of prussian-blue-analog nanocages via a direct etching method and their conversion into Ni–Co-mixed oxide for enhanced oxygen evolution. Adv. Mater. 28, 4601 (2016).
49.Avci, C., Arinez-Soriano, J., Carne-Sanchez, A., Guillerm, V., Carbonell, C., Imaz, I., and Maspoch, D.: Post-synthetic anisotropic wet-chemical etching of colloidal sodalite ZIF crystals. Angew. Chem., Int. Ed. 54, 14417 (2015).
50.Indra, A., Song, T., and Paik, U.: Metal organic framework derived materials: Progress and prospects for the energy conversion and storage. Adv. Mater. 30, 1705146 (2018).
51.Yu, X.Y., Yu, L., Wu, H.B., and Lou, X.W.: Formation of nickel sulfide nanoframes from metal–organic frameworks with enhanced pseudocapacitive and electrocatalytic properties. Angew. Chem., Int. Ed. 54, 5331 (2015).
52.Yu, L., Zhang, L., Wu, H.B., and Lou, X.W.: Formation of NixCo3−xS4 hollow nanoprisms with enhanced pseudocapacitive properties. Angew. Chem., Int. Ed. 53, 3711 (2014).
53.Su, Y., Ao, D., Liu, H., and Wang, Y.: MOF-derived yolk–shell CdS microcubes with enhanced visible-light photocatalytic activity and stability for hydrogen evolution. J. Mater. Chem. A 5, 8680 (2017).
54.Zhang, J., Yu, J., Jaroniec, M., and Gong, J.R.: Noble metal-free reduced graphene oxide-ZnxCd1−xS nanocomposite with enhanced solar photocatalytic H2-production performance. Nano Lett. 12, 4584 (2012).
55.Fan, C., Wang, X., Sang, H., and Wang, F.: Effects of composition and calcination temperature on photocatalytic evolution over from glycerol and water mixture. Int. J. Photoenergy 2012, 1 (2012).
56.Jiang, D., Sun, Z., Jia, H., Lu, D., and Du, P.: A cocatalyst-free CdS nanorod/ZnS nanoparticle composite for high-performance visible-light-driven hydrogen production from water. J. Mater. Chem. A 4, 675 (2016).
57.Li, Q., Meng, H., Zhou, P., Zheng, Y., Wang, J., Yu, J., and Gong, J.: Zn1–xCdxS solid solutions with controlled bandgap and enhanced visible-light photocatalytic H2-production activity. ACS Catal. 3, 882 (2013).
58.Wang, H., Li, Y., Shu, D., Chen, X., Liu, X., Wang, X., Zhang, J., and Wang, H.: CoPtx‐loaded Zn0.5Cd0.5S nanocomposites for enhanced visible light photocatalytic H2 production. Int. J. Energy Res. 40, 1280 (2016).
59.Dai, D., Xu, H., Ge, L., Han, C., Gao, Y., Li, S., and Lu, Y.: In situ synthesis of CoP co-catalyst decorated Zn0.5Cd0.5S photocatalysts with enhanced photocatalytic hydrogen production activity under visible light irradiation. Appl. Catal., B 217, 429 (2017).
60.Guo, X., Chen, C., Song, W., Wang, X., Di, W., and Qin, W.: CdS embedded TiO2 hybrid nanospheres for visible light photocatalysis. J. Mol. Catal. A: Chem. 387, 1 (2014).
61.Pany, S. and Parida, K.M.: A facile in situ approach to fabricate N,S-TiO2/g-C3N4 nanocomposite with excellent activity for visible light induced water splitting for hydrogen evolution. Phys. Chem. Chem. Phys. 17, 8070 (2015).


Type Description Title
Supplementary materials

Mu et al. supplementary material
Mu et al. supplementary material 1

 Word (3.0 MB)
3.0 MB


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed