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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Review

Application of MOFs-Derived Metal Sulfides and Their Composites in Photocatalysis

  • Chen Shijian 1, 2 ,
  • Pan Yuxuan 2 ,
  • Cheng Lihua 2, 3 ,
  • Qian Junfeng 1, * ,
  • Wang Hui , 2, 3, *
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  • 1 School of Petrochemical Engineering, Changzhou University, Changzhou 213000, China
  • 2 School of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming 525000, China
  • 3 Guangdong Provincial Key Laboratory of Advanced Green Lubricating Materials, Maoming 525000, China

Received date: 2023-08-15

  Revised date: 2024-01-13

  Online published: 2024-03-15

Supported by

Guangdong Science and Technology Innovation Strategy Program(2023S005054)

Abstract

With the rapid development of society and economy,the demand for energy has been continuously increasing.Solar energy has emerged as a clean energy source with great development potential,and the long-term effective utilization of solar energy has become an urgent problem that needs to be addressed.Metal-organic frameworks(MOFs)derived metal sulfides retain the original structural characteristics of their parent MOFs,including large surface areas,dispersed nanoscale subunits,and abundant active sites.They overcome the limitations of MOFs in terms of material stability at high temperatures and harsh chemical environments.Moreover,compared to metal oxides,they have a narrower bandgap,which extends their light absorption range to the visible region.The porous nature of MOFs-derived metal sulfides also provides additional pathways for light-induced electron migration,promoting charge carrier separation.As a result,they have attracted increasing attention in the field of photocatalysis.Although this field is still in its nascent stage,the results obtained so far indicate that MOF-derived metal sulfides and their composite photocatalysts have high potential for practical applications.This article systematically elucidates the synthesis,performance,and mechanisms of MOFs-derived metal sulfide photocatalysts and their composites in various application areas,such as wastewater treatment,water splitting for hydrogen generation,and CO2reduction.This will provide a new direction for the synthesis and application of novel and efficient composite photocatalytic materials.Additionally,some existing issues in current research are addressed,and the future prospects and challenges of MOFs-derived sulfide photocatalytic materials are discussed 。

Contents

1 Introduction

2 Strategies for the preparation of MOFs-derived metal sulfides

3 MOFs-derived monometallic sulfides

4 MOFs-derived polymetallic sulfides

5 MOFs-derived multicomponent metal sulfides

6 MOFs-derived oxide-sulfide composites

7 MOFs-derived carbon-based-sulfide,carbon-nitrogen-based-sulfide composites

8 Conclusion and outlook

Cite this article

Chen Shijian , Pan Yuxuan , Cheng Lihua , Qian Junfeng , Wang Hui . Application of MOFs-Derived Metal Sulfides and Their Composites in Photocatalysis[J]. Progress in Chemistry, 2024 , 36(4) : 511 -524 . DOI: 10.7536/PC230806

1 Introduction

the world's energy demand continues to increase,and its main source is fossil fuels,especially oil,coal and natural gas.However,the reserves of fossil fuels are limited.Therefore,the rational and efficient use of solar energy is the future development trend of energy utilization.However,the efficient conversion of solar radiation into chemical energy or energy-intensive liquid energy is the key to achieving large-scale solar energy output[1,2]。 At present,the light energy conversion efficiency is low due to the constraints of solar energy absorption,photogenerated carrier separation efficiency,catalytic reaction effect and other factors.Because the photogenerated electrons and holes are easy to recombine and lose energy,the key to improve the photoconversion efficiency is to continuously improve the construction system of high-efficiency and low-cost photocatalytic materials[3,4]
metal-organic frameworks(MOFs)are a class of porous crystalline materials structured by inorganic metal nodes(metal ions or metal clusters)and bridging organic linkers,which are widely used in sensing,gas storage,separation,and catalysis[5][6,7][8,9][10,11]。 MOFs have highly porous structures and open channels,which make the active sites easily accessible and greatly facilitate the transport of products[12~16]。 MOFs directly used as photocatalysts have low photocatalytic activity and poor cycle stability,while MOFs-derived metal sulfides and their composites have shown great potential in the field of photocatalysis(Table 1)。
表1 Application of MOFs-derived metal sulfides and their composites in photocatalysis

Table 1 Application of MOFs-derived metal sulfides and their composites in photocatalysis

MOFs Sample Applications Performance ref
ZIF-L ZnS Cr(VI) reduction;
X-3B degradation
100% (30 min, UV Light); 94.6% (20 min, UV Light) 17
MIL-68-In In2S3 MO degradation 97% (120 min, >420 nm) 18
Zn-MOF;
Cd-MOF
ZnS; CdS MB degradation 90.2%; 91.6% (100 min, >420 nm) 19
Sn-MOF SnS2-SnS Cr(Ⅵ) reduction 91.51% (180 min, 400~800 nm) 20
CdIF-3 BW@CdS/Cd2SO4(OH)2 H2 evolution 18420 μmol·h-1·g-1 (Pt, Lactic acid, >420 nm) 21
ZIF-8 Cd0.42Zn0.58S H2 evolution 4100 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 22
ZIF-8 Cd0.5Zn0.5S Cr(Ⅵ) reduction;
MO degradation
100% (12 min, >420 nm);
94.2% (20 min, >420 nm)
23
ZIF-67 Cu0.9Co2.1S4@MoS2 H2 evolution 40156 μmol·h-1·g-1 (TEOA, >420 nm) 24
ZIF-8 Zn0.7Cd0.3S/CdS H2 evolution 2700 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 25
Cd-MOF (Zn0.95Cu0.05)0.6Cd0.4S H2 evolution 4150.1 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 26
ZIF-67 Co3S4@Mo2S3 H2 evolution 75 μmol·h-1·g-1 (TEOA, 420 nm) 27
Ni-ZIF-67 NiS/Co3S4/ZnCdS H2 evolution 98600 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 28
Ni-MOF NiS/CdS H2 evolution 57930 μmol·h-1·g-1 (Lactic acid, 420 nm) 29
Cd-MOF NiS/Zn0.5Cd0.5S H2 evolution 16780 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 30
ZIF-8 CIZS H2 evolution;
Photo-reforming reaction
74.8 μmol·h-1·g-1 (360 nm)
AQY of α-cellulose: 28%
31
ZIF-8 ZnS/ZnIn2S4 H2 evolution 453.4 μmol·h-1·g-1 (TEOA, Xenon Light) 32
Ni-MOF-74 Cd-Ni-MOF-T/CdS/NiS H2 evolution 40080 μmol·h-1·g-1 (Lactic acid, >420 nm) 33
MIL-68(In) MnS/In2S3 CO2 reduction 58 μmol·h-1·g-1 (TEOA, Xenon Light) 34
ZIF-67 Co9S8-Mn0.05Cd0.95S H2 evolution 13369 μmol·h-1·g-1 (Na2S-Na2SO3, UV Light) 35
ZIF-67 ZnIn2S4@Co3S4 H2 evolution 4261 μmol·h-1·g-1 (TEOA, ≥350 nm) 36
ZIF-67 ZnIn2S4@CoS2 H2 evolution 2768 μmol·h-1·g-1 (TEOA, >350 nm) 37
MOF-74-Ni/Cd CdS@NiS H2 evolution 42700 μmol·h-1·g-1 (Lactic acid, 450 nm) 38
ZIF-8 ZnS@SnS2/CdS CO2 reduction 155.57 μmol·h-1·g-1 (300 ~ 1100 nm) 39
Cd-MOF CdS/MoS2 H2 evolution 5587 μmol·h-1·g-1 (Lactic acid, >420 nm) 40
Co-MOF Co4S3/CdS H2 evolution 5892.6 μmol·h-1·g-1 (Lactic acid, 420 nm) 41
ZIF-8 Sv-ZnS/ZnIn2S4 H2 evolution;
CO2 reduction
2912.3 μmol·h-1·g-1; 2075.7 μmol·h-1·g-1 (TEOA, >420 nm) 42
Mo-MOF;
Cd-MOF
MoS2/CdS H2 evolution 106729 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 43
ZIF-67 Co9S8/CdS H2 evolution 1852 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 44
Co-MOF Co4S3/CdS H2 evolution 12360 μmol·h-1·g-1 (Lactic acid, >420 nm) 45
ZIF-8 Cu/ZnS-TAA MB degradation;
MO degradation
260 mg/g (10 min, >420 nm) 46
CuZn-MOF CuS/ZnS H2 evolution 6208.6 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 47
ZIF-8 CeO2/ZnS-CuS H2 evolution 13470 μmol·h-1·g-1 (Methanol, Xenon Light) 48
ZIF-67 TiO2-Ti3C2-CoSx H2 evolution 950 μmol·h-1·g-1 (Methanol, UV-visible light) 49
ZnCo-ZIF@ZIF-8 Co3O4-ZnO@ZnS/Pt H2 evolution 3269.3 μmol·h-1·g-1(Na2S-Na2SO3, Xenon Light) 50
MOF-5 ZnO/ZnS H2 evolution 415 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 51
Mo-MOF NPC-MoS2@Bi4O5Br2 CO2 reduction 19.16 μmol·h-1·g-1 (380 nm) 52
Cd-MOF CdS/NC-500 TC degradation 83% (60 min, >420 nm) 56
Mo-MOF MoS2/CN H2 evolution 423.94 μmol·h-1·g-1 (TEOA, >420 nm) 57
ZIF-67 CoSx-C/N2@CZS H2 evolution 18570 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 58
ZIF-8 g-C3N4/ZnS MO degradation 74.40% (160 min, >420 nm) 59
CuZn-ZIF@
MIL-68(In)
Cu0.5Zn0.5In2S4-rGO
-g-C3N4
H2 evolution 11600 μmol·h-1·g-1 (Na2S-Na2SO3, >420 nm) 60
In-MOF In6S7 NPs MO degradation 88% (160 min, 400~700 nm) 61
Ni-MOF g-C3N4/C@Ni3S4/Ni2P H2 evolution 14490 μmol·h-1·g-1 (>420 nm) 62
Cu-Ni-MOF Cu2S:NiS2@C/rGO Photocatalytic C-N coupling application of phenylboronic acid and imidazole Conversion rate and selectivity > 90% 63
in this paper,the literature reports on sulfides and their composites derived from MOFs In the past five years are systematically reviewed,including monometallic sulfides,multicomponent metal sulfides,multicomponent metal sulfids,oxide-sulfide composites,carbon-sulfide composites and carbon-nitrogen-sulfide composites derived from MOFs。

2 Preparation Strategy of MOFs Derived Metal Sulfide

Using MOFs as precursors or templates,the developed sulfides derived from MOFs retain the original structural characteristics of the parent MOFs,with large surface area,dispersed nano-sized subunits and abundant active sites,after simple inert gas pyrolysis,air annealing,solvent thermal dissolution,ion exchange or in-situ sulfidation(Figure 1).it overcomes the limitation of raw material stability of MOFs at high temperature and harsh chemical environment.Compared with oxides,It has a narrower band gap,which extends Its optical absorption range to the visible region.its porous nature may provide an additional pathway for the migration of photoexcited electrons,thereby facilitating charge carrier separation。
图1 MOFs衍生硫化物制备策略图

Fig. 1 Diagram of MOFs-derived sulfide preparation strategy

3 MOFs derived monometallic sulfide

The synthesis method of MOFs-derived monometallic sulfides is simple,the synthesis path is easy to control,and the original structural characteristics of MOFs(with larger specific surface area and more active site pore structure)are retained.The metal element or morphology of metal sulfides can be precisely controlled by screening appropriate MOFs precursors and heat treatment methods.However,due to the great influence of material properties,there are few reports,and some redox active metal sulfides,such as ZnS,In2S3and SnS2,are mainly used in the field of photocatalysis 。
Li et al.Used thioacetamide(TAA)to sulfurize rod-like ZIF-L to obtain porous tubular ZnS,and further studied the effects of different sulfurization time on the photocatalytic reduction of Cr(Ⅵ)and dye degradation by ZnS[17]。 The results showed that when the sulfidation time was 3 H,the catalytic performance of ZnS was the best,that is,ZnS-3 could achieve 100%reduction of Cr(Ⅵ)within 30 min under UV irradiation,and the highest degradation rate of reactive red(X-3B)was 94.6%within 20 min.The effects of different reaction conditions on the photocatalytic performance were studied,and the results showed that ZnS-3 showed good photocatalytic performance for the reduction of Cr(Ⅵ)under weak acidic and neutral conditions.The position of the conduction band(CB)is higher than the redox potential of the O2/·O2,and the generated superoxide radical(·O2)can promote the reduction of Cr(Ⅵ)to Cr(Ⅲ)and the oxidation of X-3B.The valence band(VB)hole and the H2O are oxidized to generate hydroxyl radical(·OH),which reduces the probability of electron-hole recombination and promotes the photocatalytic reaction 。
Fang et al.Prepared invaginated hexagonal In2S3nanorods with hollow structure by liquid phase sulfidation method using MIL-68(In)as precursor[18]。 The effect of different curing time on the photodegradation of dye by In2S3was further studied,and the results showed that the In2S3-8 h exhibited excellent photodegradation performance,and the degradation rate of anionic dye methyl orange(MO)was 97%(within 120 min)under visible light.The lowest unoccupied molecular orbital(LUMO)and the highest occupied molecular orbital(HOMO)of MO molecule are localized in the semiconductor band gap(Eg)of In2S3due to the good adsorption ability of In2S3,forming a cross-band arrangement(type I).The transfer of photogenerated electrons and holes from In2S3to MO molecules is beneficial to the generation of more free radicals under the action of contact electric field,h+can directly oxidize pollutants,and photogenerated electrons can reduce O2to generate·O2active substances and further degrade pollutants to improve the photodegradation performance 。
Li et al.Prepared ZnS@C and CdS@C composites by one-pot sulfidation method using Zn-MOF and Cd-MOF as precursors,respectively,and obtained pure ZnS and CdS catalysts by removing carbon substances by high temperature pyrolysis[19]。 One-pot sulfidation of The MOF precursor can suppress the sintering phenomenon during the stepwise carbonization-sulfidation process.the results showed that about 90.2%and 91.6%of cationic dye methylene blue(MB)was degraded by ZnS and CdS,respectively,after 100 min。
Dai et al.Used Sn-MOF as precursor to prepare SnS2-SnS composite by pyrolytic sulfidation method[20]。 The ratio of SnS2to SnS was adjusted by changing the ratio of MOF to sulfur powder and the pyrolysis temperature.The reduction rate of Cr(Ⅵ)reached 91.51%after the catalyst was irradiated by visible light(400~800 nm)for 3 H.The higher catalytic activity is mainly due to the fact that the CB of SnS2is more negative than that of SnS and the VB of SnS2is more positive than that of SnS,and the photogenerated carriers generated by illumination will be transferred from the SnS2wide band gap semiconductor to the SnS narrow band gap material,thus promoting the separation of photogenerated carriers 。
The butterfly wing(BW)has a porous hierarchical structure that exhibits efficient light harvesting capability,and the wing scales can use internal reflection to harvest light,which means that the unique structure of BW is an effective solar collector.The combination of BW with the abundant exposed metal sites of MOFs further improved the light absorption ability and suppressed the aggregation of active sites during sulfuration.Zhong et al.Deposited cadmium carbonate(NC)doped with cadmium nitrate on the surface of BW to obtain BW@NC,and then directly grew Cd-based MOF(CdIF-3)on the surface of BW@NC to prepare BW@NC@CdIF-3 with a network hierarchical structure(Fig.2),which was used as a sacrificial template to prepare BW@SS deposited with CdS/Cd2SO4(OH)2nanoparticles through a simple vulcanization process[21]。 The effect of co-catalyst on the photocatalytic activity of BW@SS was further investigated.The results show that the hydrogen evolution rate of BW@SS under visible light(room temperature)with Pt as the cocatalyst is 18420μmol·h-1·g-1,and the hydrogen evolution rate without the cocatalyst is 3376μmol·h-1·g-1.The excellent performance of BW@SS photocatalyst can be attributed to the enhanced light harvesting,higher conduction band,and efficient transfer of photogenerated charge carriers.The doped Cd2SO4(OH)2can be reduced to metal Cd as an electron trap,thereby improving the charge separation efficiency and further enhancing the hydrogen production performance of CdS 。
图2 具有网状分层结构的BW@NC、BW@NC@CdIF-3和BW@SS合成示意图[21]

Fig. 2 Illustration of the fabrication of BW@NC, BW@NC @CdIF-3, and BW@SS with reticular hierarchical structure[21]

At present,MOFs-derived monometallic sulfide materials are basically prepared by solvothermal vulcanization,which has more advantages in photocatalytic degradation system,but the cycle stability in photocatalytic reaction still needs to be improved.Due to the limited variety,it may be necessary to combine other metal materials to improve its photocatalytic performance。

4 MOFs derived multicomponent metal sulfide

Multicomponent metal sulfides,(MxNyS),templated by multimetallic(M=Co,Zn,Cd,Cu,etc.)MOFs usually have the advantages of more active sites,larger specific surface area,higher conductivity,and unique mesoporous structure(shortened electron transport path).Multicomponent metal sulfides derived from MOFs are generally synthesized by sulfidation of homogeneous bimetallic MOFs formed by introducing different metal ions into a single framework.Multicomponent metal sulfides refer to metal sulphides with two or more different metal cations,which is different from the physical mixture of two or more metal sulphides 。
Homogeneous bimetallic MOFs formed by introducing different metal ions into a single framework have a large surface area,which can combine multiple active sites,thereby improving the photocatalytic performance.Mu et al.Used ZnCd-ZIFs obtained by introducing Cd into ZIF-8 as a self-template to prepare mesoporous CdxZn1−xS polyhedra by in situ sulfurization[22]。 The Cd/Zn ratio was adjusted by changing the Cd content,and the CZS showed the optimal hydrogen evolution rate(4.10 mmol·h-1·g-1)under visible light when Cd/Zn=0.42/0.58.The balance between CB potential and band gap width,the fast carrier separation and migration ability,and the high surface area of the photocatalyst facilitate the photocatalytic reaction 。
Bimetallic sulfide photocatalysts with porous hollow structure and enhanced photocatalytic performance can be prepared by using appropriate MOFs as templates and exogenous metals because of their unique inherent voids,huge surface area and surface permeability.Doping the second metal to MOFs can increase the catalytic active sites and improve the electrical conductivity,thereby improving the photocatalytic activity.Wu et al.Prepared 3D hollow structured Cd0.5Zn0.5S(CZS-X)nanocages using rhombohedral dodecahedron ZIF-8 as precursor and thioacetamide(TAA)as sulfur source at different sulfurization times[23]。 The results show that CZS-3 with a curing time of 3 H exhibits the best photocatalytic activity under visible light,and has good recycling performance and stability.In the photocatalytic reduction of Cr(Ⅵ),CZS-3 showed the highest reduction efficiency(100%in 12 min),and in the photocatalytic MO oxidation,CZS-3 also showed the highest efficiency(94.2%in 20 min and 94.5%in 30 min).The CB redox potential of CZS-3 is higher than that of O2/·O2-,so it can produce·O2-radicals to reduce Cr(Ⅵ).H2O2reacts with e-to produce·OH,which can degrade MO.The Cd0.5Zn0.5S from ZIF-8 has larger specific surface area and more exposed active sites,so it has outstanding photocatalytic performance 。
Ma et al.Used the bimetallic Cu/Co-MOFs obtained by introducing Cu into ZIF-67 as the precursor to synthesize the nanoflower hybrid structure CuxCo(3−xS4@MoS2composite material in situ through hydrothermal reaction(Fig.3),and further studied the effect of different Cu ion doping amounts on the photocatalytic performance[24]。 The results indicated that the composite exhibited efficient catalytic hydrogen production at a rate of 40 156μmol·h-1·g-1under visible light without additional noble metals and semiconductors as co-catalysts.Upon photoelectron excitation(420 nm),electrons are excited from the VB of the Cu0.9Co2.1S4@MoS2to the CB,and from the HOMO of the EY molecule to the LUMO.Triethanolamine(TEOA)reduction quenches the excited EY(*EY)to produce EY•−.Electrons are transferred from EY•−to the CB of Cu0.9Co2.1S4@MoS2,and H+is reduced to form H2
图3 Cu0.9Co2.1S4@MoS2结构示意图[24]

Fig. 3 Schematic structure of Cu0.9Co2.1S4@MoS2[24]

The heterostructure can effectively inhibit the recombination of photogenerated charge carriers and reduce the photocorrosion phenomenon in the presence of supported photocatalysts.Bai et al.Used ZIF-8 as a precursor to synthesize Zn1−xCdxS/CdS quantum dot heterojunction materials by low temperature sulfurization and cation exchange[25]。 The Zn/Cd ratio was adjusted by changing the amount of CdS added.The results show that the photocatalytic hydrogen production rate of the Zn0.7Cd0.3S/CdS quantum dot material under visible light irradiation is optimal to reach 2.7 mmol·h-1·g-1without any noble metal co-catalyst.The VB photogenerated holes of CdS migrate to the local acceptor state of Zn0.7Cd0.3S,while the CB photogenerated electrons of Zn0.7Cd0.3S transfer to CdS.The photoexcited carriers formed by the Zn0.7Cd0.3S/CdS heterostructure can significantly inhibit the electron-hole recombination,which originates from the irreversible hole-driven oxidation reaction in CdS photocatalyst,which can effectively inhibit the photocorrosion of photogenerated carriers,thus promoting the photocatalytic reaction 。
Broader solar absorption and more efficient photoexcited charge separation can be achieved by fine-tuning the band gap.Solid solution catalysts have stronger electronic attraction and tighter interface,which can achieve higher interfacial charge transfer efficiency and thus improve the photocatalytic hydrogen evolution activity.Liu et al.Used Zn and Cu-doped Cd-MOF as precursors to obtain uniformly distributed solid solution(Zn0.95Cu0.051−xCdxS by solvothermal method and high temperature calcination[26]。 On the basis of a certain molar ratio of Zn and Cu,the composition of(Zn0.95Cu0.051−xCdxS can be well controlled by changing the proportion of Cd,so as to fine-tune the conduction band edge to obtain the optimal hydrogen evolution rate.Under visible light,the optimized(Zn0.95Cu0.050.6Cd0.4S showed high stability,and its photocatalytic hydrolysis hydrogen production rate was 4150.1μmol·h-1·g-1
At present,MOFs-derived multi-metal sulfide materials are basically prepared by doping a second metal ion in a single MOFs sulfurization derivation process,and have higher catalytic activity and better cycle stability compared with single metal sulfides.the synergistic effect of two or more metals makes the multi-metal sulfides have rich redox active site mesoporous structure,and the synergistic effect is also reflected in the significant inhibition of electron-hole recombination。

5 MOFs derived multicomponent metal sulfides

In recent years,researchers at home and abroad have prepared multi-component metal sulfide nanocomposites for the synthesis of photocatalysts to improve their photocatalytic performance.Multicomponent metal sulfides(MxS/NyS)templated by metal(M=Co,Zn,Cd,Cu,Ni,In,etc.)MOFs generally integrate two or more functional materials with strong synergistic effect,which enhances the photocatalytic activity and structural stability of each component 。
The inherited porous structure of MOFs-derived metal sulfides can be used as a heterostructure constructed by combining guests or hosts with other metals or inorganic nanoparticles,and the regulation of energy band position is beneficial to the photocatalytic reaction.Li et al.Used ZIF-67 as a synthesis template to synthesize rhombic dodecahedron Co3S4@Mo2S3composite with hollow structure by one-step continuous hydrothermal method after introducing S and Mo elements[27]。 The effects of the amount of ZIF-67,the amount of Na2MoO4·2H2O and TAA solution and different reaction conditions on the activity of the catalyst were studied.The results showed that the Co3S4@Mo2S3-9(SBET=47 m2·g-1)with 9 mL Na2MoO4·2H2O and 9 mL TAA solution had the best photocatalytic hydrogen evolution performance(375.37μmol,5 H)under 420 nm light irradiation and pH=9.The contact between the Co3S4and the Mo2S3causes band bending,which further promotes the recombination of holes at the interface of the Co3S4and electrons on the CB of the Mo2S3.The simultaneous formation of a built-in electric field from Co3S4to Mo2S3can facilitate electron transfer.The S-type heterojunction formed by Co3S4,Mo2S3can maintain a more effective redox potential 。
Huang et al.Prepared a series of Z-type NiS/Co3S4/ZnCdS photocatalysts by sulfidation modification using two-dimensional Ni-ZIF-67 as a template,and discussed the effects of Ni-ZIF-67:S powder ratio,annealing temperature,and the addition of NiS/Co3S4on the performance of the catalysts,respectively.The results showed that under illumination(>420 nm),the best hydrogen evolution rate of NiS/Co3S4/ZnCdS was 98.6 mmol·h-1·g-1when the Ni-ZIF-67:S powder ratio was 1:2,the annealing temperature was 600°C,and the addition of NiS/Co3S4was 20 mg[28]。 The synergistic effect between the heterojunction formed by ZnCdS and NiS/Co3S4is beneficial to electron transfer and carrier generation,which inhibits the agglomeration of ZnCdS nanoparticles and exposes more active sites,and the combination of NiS/Co3S4and ZnCdS narrows the band gap and improves the utilization of light absorption 。
Su et al.Synthesized NiS/CdS composite using Ni-MOF and cadmium salt as raw materials by one-step hydrothermal vulcanization[29]。 The effect of Ni-MOF synthesized with different organic ligands on the catalytic activity of NiS/CdS was further studied,and the results showed that the NiS/CdS composite derived from Ni(TPA)-MOF with terephthalic acid(TPA)as the organic ligand had the best hydrogen evolution rate,which could reach 57.93 mmol·h-1·g-1under 420 nm light irradiation.The better catalytic activity is due to the fact that the organic ligand group and the electronegativity of Ni-MOF provide effective attachment sites for Cd precursor and CdS;The dynamic coordination interaction between Ni-MOF and Cd ions/CdS plays a role in regulating the uniformity and heterojunction of NiS/CdS composites,and leads to the change of conduction band position,which in turn improves the photocatalytic performance 。
Zhao et al.Fabricated heterojunctions by solvothermal sulfidation and thermal annealing using Zn and Ni-doped Cd-MOF as precursors NiS/ZnxCd1−xS(Fig.4 )[30]。 By adjusting the concentration of doped metal in MOFs,the chemical composition and band gap of the heterojunction can be fine-tuned to further optimize its light absorption capacity and photocatalytic activity.The results show that the optimal hydrogen evolution rate of NiS/Zn0.5Cd0.5S is 16.78 mmol·h-1·g-1under visible light irradiation(λ>420 nm),and it has high stability and recyclability.In charge transport,the Zn0.5Cd0.5S region potential is higher and the NiS region potential is lower,which makes the photogenerated charge transfer from Zn0.5Cd0.5S to NiS,providing electrons to reduce the adsorbed H+
图4 NiS/ZnxCd1−xS的制备过程示意图[30]

Fig. 4 Schematic illustration of the preparation procedure of NiS/ZnxCd1−xS[30]

Nagata et al.Prepared Cu,In-doped ZnS(CIZS)by hydrothermal method using Cu,In-doped ZIF-8 as precursor(Fig.5)[31]。 The effect of different amounts of Cu and In on the photocatalytic activity of CIZS was further studied.The results showed that the photocatalyst prepared by adding 1%Cu and 1%In in the synthesis process had the highest activity.Under 360 nm light irradiation,the hydrogen evolution rate is 74.8μmol·h-1·g-1,and the AQY ofα-cellulose photoreforming reaction is as high as 28%.The CIZS band gap is narrowed by Cu and In doping so that the redox potential is sufficient for the photoreforming reaction 。
图5 CIZS的合成示意图[31]

Fig. 5 Schematic diagram of the synthesis of CIZS[31]

The formation of that heterostructure can generate a strong built-in electric field to promote charge separation;The construction of hierarchical nanostructures can increase the specific surface area of the catalyst,enhance the light harvesting ability of the catalyst,and thus improve the photocatalytic activity.Song et al.Prepared nanocomposite ZnS/ZnIn2S4heterojunction by sulfidation of ZIF-8 and in-situ precipitation of ZnIn2S4in a one-pot hydrothermal method[32]。 The mass ratio of ZIF-8 to ZnIn2S4was adjusted by changing the amount of ZIF-8 added.The results showed that the ZnS/ZIS-20 exhibited excellent photocatalytic activity for hydrogen production under xenon light irradiation at a ZIF-8 to ZnIn2S4mass ratio of 20%,and the optimal hydrogen production rate was 453.4μmol·h-1·g-1.The photogenerated electron on the CB of ZnIn2S4easily migrates to the CB of ZnS due to its more negative potential;At the same time,the holes on the VB of ZnS can flow to the VB of ZnIn2S4due to its large positive potential,and this heterojunction effective interface transfer is the main reason for the improvement of photocatalytic efficiency of ZnS/ZIS 。
Wang et al.Prepared a series of hierarchical Cd-Ni-MOF micro/nanostructures assembled by nanosheets and nanorods by a two-step solvothermal method through partial substitution of Cd2+for Ni2+in the Ni-MOF-74 structure[33]。 Hierarchical Cd-Ni-MOF-T/CdS/NiS hybrid micro/nanostructured materials were then prepared by sulfidation of Cd-Ni-MOF.The effect of ethanol∶DMF on the catalytic performance was further studied.The results showed that when the ratio of ethanol to DMF was 1∶1,the prepared catalyst showed the best photocatalytic hydrogen evolution performance,which was about 40.08 mmol·h-1·g-1.The p-n heterojunction between CdS and NiS facilitates the transfer of photogenerated electrons from the CB of NiS to that of CdS,and the heterojunction between CdS and Cd-Ni-MOF-T further promotes the transfer of electrons from the CB of CdS to that of Cd-Ni-MOF-T,resulting in the effective separation of photogenerated carriers 。
Tan et al.Impregnated Mn2+In MIL-68(In)submicron rods to make MnS/In2S3nanosheet composite photocatalyst by further sulfurization process[34]。 By controlling the amount of Mn2+injected into MIL-68(In),a series of MnS/In2S3p-n heterojunctions with tunable mass percentage can be fabricated.The photocatalytic activity of MnS/In2S3increases gradually with the increase of MnS mass fraction,and at MnS/In2S3(30 wt%),the optimal CO formation rate is 58μmol·h-1·g-1.The better reduction rate of CO2is due to the dispersion of Mn2+and In3+in the template,and a large number of MnS/In2S3small p-n heterojunctions can be simultaneously generated in each layered particle.Under light irradiation,the In2S3side will accumulate photogenerated electrons for CO2reduction,while the photogenerated holes will accumulate on the MnS side and be consumed by TEOA in turn,thus establishing a static charge balance in the photocatalytic system 。
Su et al.Sulfided and calcined ZIF-67 as a precursor to obtain Co9S8,and Co9S8and Mn0.05Cd0.95S were used to prepare Co9S8-MCS composite catalyst by hydrothermal method(SBET=13 m2·g-1)(Fig.6 )[35]。 The effect of different Co9S8addition on the photocatalytic performance was further studied,and the results showed that when Co9S8∶Mn0.05Cd0.95S=1∶10,the hydrogen evolution rate of Co9S8-MCS composite catalyst was the best,which was 13.369 mmol·h-1·g-1under simulated sunlight.Beside,that Co9S8-MCSstill has good hydrogen evolution stability after four cycle.The CB and VB of Co9S8are between those of MCS,so the Co9S8-MCS composite catalyst has a suitable redox ability for photocatalytic reaction.Co9S8-MCS have strong light harvesting ability,abundant reaction sites and heterostructure to promote charge separation and transfer 。
图6 Co9S8-MCS的合成示意图[35]

Fig. 6 Schematic diagram of the synthesis of Co9S8-MCS[35]

Wang et al.Prepared ZnIn2S4@Co3S4(SBET=90.4 m2·g−1)by hydrothermal method using ZIF-67 as a sacrificial template[36]。 The effect of the amount of Co3S4on the photocatalytic performance was further studied,and the results showed that when the amount of Co3S4was 5%,the hydrogen production rate of ZnIn2S4@Co3S4was the best(4261μmol·h-1·g-1) 。
Xi et al.Prepared ZnIn2S4@CoS2heterostructure(SBET=48~60 m2·g−1)by a facile hydrothermal method using ZIF-67-derived Co3O4as precursor[37]。 The molar ratio of Co3O4to ZnIn2S4was adjusted by controlling the amount of Co3O4added.Under simulated solar irradiation,the ZnIn2S4@CoS2heterojunction with 5%CoS2content(ZC-5)showed the optimal photocatalytic hydrogen evolution performance with a hydrogen production rate up to 2768μmol·h-1·g-1.Heterostructure was formed at the interface between ZnIn2S4and CoS2,Co3S4,which promoted the electron transfer and inhibited the recombination of electron-hole pairs,thus improving the photocatalytic hydrogen production activity of the composite 。
Bimetallic MOFs can be used as precursors/templates for the preparation of photocatalysts due to their adjustable composition and diverse structures,while they can also form tight heterojunctions to promote the separation of photoexcited charge carriers and further improve the photocatalytic hydrogen evolution rate.Liu et al.Prepared MOF-74-Ni/Cd by introducing cadmium ions into MOF-74-Ni through ion exchange method,and used it as a precursor to synthesize CdS@NiS photocatalyst by one-step hydrothermal method[38]。 Further comparing the catalytic activity of CdS@NiS derived from MOFs with that of CdS-NiS and CdS/NiS prepared from pure CdS,the results show that the photocatalytic hydrogen evolution rate of CdS@NiS at 450 nm is 42.7 mmol·h-1·g-1and the AQY is 13.23%,while the hydrogen evolution rate of CdS-NiS and CdS/NiS is only 1.727 and 2.258 mmol·h-1·g-1.The heterointerface formed by the effective combination of CdS and NiS in CdS@NiS(interface synergy effect)promotes the separation and migration of charge carriers,thus greatly accelerating the proton reduction reaction 。
Zhao et al.Used ZIF-8 as a precursor to sulfurize and synthesize hollow ZnS polyhedral cages,which were further coated with SnS2nanosheets[39]。 The obtained ZnS@SnS2heterostructure cage is decorated by CdS quantum dots to obtain the ZnS@SnS2/CdS material(SBET≈86.5 m2·g−1).The theoretical weight percentage of ZnS:ZnS@SnS2was adjusted by changing the amount of ZnS added,and the effect of soaking time of ZnS@SnS2in CdCl2solution on the catalytic performance was further studied.The results showed that when the ZnS∶ZnS@SnS2was 35%and the immersion time was 10 min,the properties of the ZnS@SnS2/CdS composite were the best,the CO generation rate was 155.57μmol·h-1·g-1,and the selectivity was 80.4%.Suitable energy level matching among ZnS,SnS2,and CdS can enable two-channel charge transfer and generate more electrons to participate in the CO2photoreduction reaction 。
The formation of effective heterostructure,the introduction of cocatalyst,the addition of sacrificial agent and the formation of sulfur vacancy are important means to improve the photocatalytic activity.Lin et al.Coated Cd-MOF on the surface of MoS2flower to construct a core-shell structure MoS2@Cd-MOF[40]。 Using TAA as sulfur source,MoS2@Cd-MOF was sulfurized to form CdS/MoS2heterojunction.The molar ratio of CdS was adjusted by changing the CdS loading on the surface of MoS2.The results showed that under UV-Vis irradiation,when CdS:MoS2=0.6∶1,the hydrogen evolution performance of CdS/MoS2was the best(5587μmol·h-1·g-1).The conduction band minimum(CBM)of MoS2in the heterojunction is lower than that of CdS,and photoexcited electrons are transferred from CdS to MoS2.MoS2as a co-catalyst can capture CdS photoexcited electrons for photocatalytic hydrogen evolution 。
Huang et al.Prepared Co4S3nanosheets from flaky two-dimensional Co-MOF by sulfurization and annealing,and synthesized Co4S3/CdS by hydrothermal method[41]。 The effect of the amount of Cd(CH3COO)2·2H2O on the performance of the catalyst was further investigated.When the dosage of Cd(CH3COO)2·2H2O is 2 mmol,the optimal hydrogen evolution rate of Co4S3/CdS is 5892.6μmol·h-1·g-1under the irradiation of 420 nm light.A typical typeⅡheterojunction structure was formed between Co4S3and CdS,which effectively promoted the separation and migration of charge carriers,and the sacrificial agent lactic acid captured the holes of CdS in VB and inhibited the charge recombination,thus enhancing the photocatalytic activity 。
Using ZIF-8 as a sacrificial template,Liu et al.Synthesized Sv-ZnS/ZnIn2S4heterostructures with sulfur vacancies by in situ sulfurization[42]。 The as-prepared Sv-ZnS/ZIS has an AQY of 19.8%±1.0%at 420 nm,a hydrogen evolution rate of 2912.3±185.9μmol·h-1·g-1,a CO yield of 2075.7±63.0μmol·h-1·g-1,and a selectivity of 93.0%±0.8%.When Sv-ZnS and ZnIn2S4form a close contact interface,electrons will spontaneously flow from Sv-ZnS to ZIS,and this charge redistribution leads to the bending of the band edges of Sv-Zn and ZIS and the formation of an IEF with an orientation pointing from ZIS to Sv-Zn.IEF,band edge bending and Coulomb force accelerate the recombination of electrons in CB in SV-ZnS with holes in VB in ZIS under visible light irradiation 。
Shi et al.Successfully prepared MoS2/CdS composite photocatalyst by in situ sulfidation method using Mo-MOF and Cd-MOF as dual precursors[43]。 The effect of the weight percentage of MoS2on the catalytic performance of MoS2/Cd was further investigated,and the results showed that the best hydrogen evolution rate of 1%MoS2/CdS was 106 729μmol·h-1·g-1.A large number of sulfur vacancies are introduced into the composite material to capture electrons as sulfur vacancy energy levels,thereby increasing the number of active sites for photocatalytic reaction 。
The morphology control of photocatalyst and the addition of sacrificial agent are effective ways to improve the activity of photocatalyst.Cheng et al.Used ZIF-67 as a template to synthesize lollipop-like Co9S8/CdS nanocomposites by direct annealing[44]。 The effect of different annealing temperatures on ZCC was further investigated in nitrogen atmosphere.The results show that ZCC-600 has the best hydrogen production rate 1852μmol·h-1·g-1under visible light at 600°C annealing temperature.Under illumination,Co9S8and CdS simultaneously produce excited state electrons that can be transferred from VB to CB,leaving holes in VB,and the electrons in the CB of CdS can migrate to the VB of Co9S8,accelerating the separation of electrons and holes between the two bands.The holes accumulated in the VB of CdS can be continuously oxidized and consumed,further promoting carrier separation 。
Kumar et al.Used Co-MOF as a precursor to prepare hollow structure Co4S3/CdS by a simple synthesis method[45]。 The effects of the mass fraction of Co4S3and the concentration of lactic acid in the Co4S3/CdS on the catalytic performance were further studied.When Co4S3is 6.0 wt%and lactic acid reaches 3 mL in 15 mL reaction solution,the optimal level is obtained,and the hydrogen evolution rate Co4S3/CdS under visible light is 12360μmol·h-1·g-1.The semiconductor CdS in Co4S3/CdS is excited by sunlight to generate electron-hole pairs in CB and VB,respectively,and the excited electrons are transferred to the Co4S3and effectively separate the photogenerated holes,followed by the reduction of protons to H2.The sacrificial agent(lactic acid)is oxidized by photogenerated holes in the VB of CdS,inhibiting electron-hole recombination 。
The photoinduced electron transfer and separation can be promoted by the addition of photogenerated electron capture agent,the construction of electron traps and the introduction of co-catalyst,which can improve the photocatalytic activity.Xiong et al.Obtained nanomaterials Cu/ZnS-SS and Cu/ZnS-TAA by reacting sodium sulfide(SS)and TAA with ZIF-8 doped with Cu2+at different Cu/Zn molar ratios under solvothermal conditions[46]。 The results of catalytic experiments show that Cu/ZnS-20-SS(SBET=43 m2·g-1)has a good photocatalytic degradation rate within 1 H,the degradation rate can reach more than 90%,and it can be reused for 4 times without obvious loss of activity.The adsorption study showed that Cu/ZnS-TAA(SBET=129~135 m2·g-1)could rapidly adsorb MB and MO,with a high adsorption capacity of about 260 mg/G in 10 min,and could reach a saturation adsorption capacity of about 300 mg/G.Since the photocathode reaction is accelerated by the addition of the photogenerated electron capture agent,the efficiency of photogenerated electron-hole separation is further improved,and the formation of photogenerated holes is accelerated(Fig.7),thus improving the photocatalytic reaction 。
图7 Cu/ZnS中的能带结构和电子空穴对分离示意图[46]

Fig. 7 Schematic diagram of the energy-band structure and electronhole pair separation in Cu/ZnS[46]

Using CuZn-MOF as precursor,Lu et al.Successfully prepared porous CuS/ZnS microspheres(SBET=22.3 m2·g−1)through rational design and low-cost sulfidation process[47]。 The ratio of Cu/Zn was adjusted by changing the addition of Cu(NO3)2·3H2O.The results showed that when the theoretical molar ratio of Cu/Zn was 3 mol%,the hydrogen production rate of CuS/ZnS under visible light reached the optimum of 6208.6μmol·h-1·g-1,and the apparent quantum yield(AQY)at 420 nm was 8.5%.The excellent photocatalytic hydrogen evolution activity is attributed to the fact that under visible light irradiation,electrons are directly excited from the VB of ZnS into the CuS cluster,and the transferred electrons lead to partial reduction of CuS to Cu2S.The CuS/Cu2S cluster can be used as an electron trap and a co-catalyst to promote the transfer and separation of photoinduced electrons.The photogenerated electrons in the CuS/Cu2S cluster transferred from the VB of ZnS can reduce the adsorbed H+to H2
MOFs-derived multi-component metal sulfide materials have a hybrid structure of two or more metal sulfides,which usually have rich mesoporous structure and strong coordination.the photocatalytic performance of the heterojunction structure formed by MOFs derived multi-component metal sulfides is greatly improved compared with that of the single-component structure,which is attributed to the energy level difference between the two structures,which enhances the absorption of visible light and promotes the separation of photogenerated charges.MOFs-derived multi-component metal sulfide partial materials(such as Co-MOFs-derived multi-component metal sulfides)have the problem of poor cycle stability without adding sacrificial agents。

6 MOFs derived oxide-sulfide composite

The MOFs derived oxide-sulfide composite material uses MOFs as a precursor to simultaneously retain two components of metal oxides and metal sulfides by controlling carbonization conditions to form MxS/MyO nanomaterials;MxS/NyO nanocomposites can also be formed by doping metals in MOFs by controlling the calcination conditions.The oxide-sulfide composite material integrates the advantages of the two,the introduction of the sulfide improves the dispersion of the oxide and exposes more active sites,and the heterojunction formed by the oxide/sulfide can effectively broaden the light absorption range,thereby improving the photocatalytic performance 。
The multi-component system formed by the heterojunction with the highly porous morphology of the genetic parent MOFs and the cocatalyst and conductive materials can promote the separation of photogenerated carriers,obtain more catalytic sites,and improve the charge transport rate.Wang et al.Prepared a CeO2/ZnS heterojunction using Ce-doped ZIF-8 as a precursor,and then used an in situ cation exchange method to load the co-catalyst CuS onto the CeO2/ZnS composite to obtain CeO2/ZnS-CuS(SBET=156.076 m2·g-1[48]。 The effect of Ce content on the catalytic performance was further studied,and the results showed that when the Ce content was 10 wt%,the photocatalytic hydrogen production performance of CeO2/ZnS-CuS was the best,which could reach 13.47 mmol·h-1·g-1.Because the CB of CeO2is more negative than that of ZnS,when the sunlight is irradiated,the electron on the CB of CeO2is transferred to ZnS,the electron on the CB of ZnS is captured by the co-catalyst CuS,and the electron reacts with H+to produce H2.The addition of the supported cocatalyst CuS and the heterojunction form a ternary system,and the regular porous dodecahedron structure of the genetic ZIF-8 provides larger specific surface area,more active sites and more effective electron transport for the photocatalytic reaction 。
Zhao et al.Designed and synthesized ternary noble metal-free TiO2-Ti3C2-CoSxheterostructures with nanocrystal size by a simple solvothermal method using ZIF-67 as a template and Ti3C2as a conductive material[49]。 The effects of the molar ratio of CoSxand the content of Ti3C2on the activity of the catalyst were further studied,and the results showed that when the molar ratio of CoSxreached 1 wt%,When the content of Ti3C2is 0.5 wt%,the best hydrogen evolution performance of TiO2-Ti-C2-CoSxis 0.95 mmol·h-1·g-1.The co-loading of CoSxand Ti3C2showed a synergistic effect in promoting the photocatalytic hydrogen production activity.That is,the introduction of the CoSximproves the dispersion of the TiO2and increases the number of exposed active sites;CoSxcan promote charge separation and provide active sites for hydrogen production due to its lower CB and electrocatalytic HER overpotential;Ti3C2can improve the conductivity of the heterostructure and facilitate the charge transport 。
Wang et al.Used the designed and synthesized bimetallic ZnCo-ZIF@ZIF-8 hybrid as a precursor to prepare Co3O4-ZnO@ZnS/Pt catalyst by simple calcination,sulfidation,and photodeposition methods[50]。 Under the irradiation of 300 W xenon lamp,the hydrogen production activity of Co3O4-ZnO@ZnS/Pt using sacrificial agent Na2S-Na2SO3was significantly improved,and the hydrogen production rate could reach 3269.3μmol·h-1·g-1.The structural analysis shows that Co3O4is highly dispersed in the ZnO@ZnS heterostructure,which effectively collects the photogenerated holes and greatly suppresses the photogenerated charge recombination,while the porous structure of Co3O4-ZnO@ZnS is beneficial to charge transfer and reduces the reactant diffusion limit 。
The nanoheterojunction structure can reduce the mean free path of charge carriers and improve the charge separation efficiency,thus significantly improving the HER activity of the catalyst under visible light.Zhao et al.Used MOF-5 as the precursor and TAA as the sulfur source,and the formation of ZnO/ZnS nanoheterojunction(Fig.8)could be adjusted by controlling the calcination temperature and time.The results showed that the optimal hydrogen evolution performance of ZnOS-30 with a treatment time of 30 min was 415µmol·h-1·g-1,and it had high stability and cyclicity without any co-catalyst[51]
图8 ZnO/ZnS 的制备过程示意图[51]

Fig. 8 Schematic illustration of the preparation procedure of ZnO/ZnS[51]

The formation of p-n heterojunction can effectively broaden the range of light absorption,inhibit electron-hole recombination,and accelerate the rate of charge transfer,thereby improving the activity of photocatalytic reduction of CO2.Sun et al.Anchored Bi4O5Br2nanosheets on the surface of Mo-MOF-derived 1D NPC-MoS2nanorods to prepare a series of hierarchical MOF-derived NPC-MoS2@Bi4O5Br2heterostructure(SBET=48 m2·g−1)by solvothermal method[52]。 The effect of NPC-MoS2loading on the photocatalytic performance was further investigated,and the results showed that the optimal loading of NPC-MoS2was 5 wt%,at which the yield of CO and CH4reached 95.8 and 159.9μmol·g-1,respectively,within 5 H.At the same time,the catalyst still showed good stability and regenerability after four cycles.Upon illumination,the photoinduced electrons of NPC-MoS2and Bi4O5Br2are excited to the CB,while the holes remain on their VB.Due to the internal electric field of the p-n heterojunction,the photoelectron is transferred to the CB of Bi4O5Br2,which is more negative than the reduction potential of CO2/CO and CO2/CH4.At the same time,holes are retained on the VB of NPC-MoS2,which has a higher oxidation potential than(CH32CHOH/CH3COCH3.Therefore,isopropanol can be oxidized to produce H+and acetone.Finally,H+reduces CO2to CO and CH4
MOFs-derived oxide-sulfide composites overcome the disadvantages of large band gap and photocorrosion of oxides,and improve the light absorption range and photocatalytic performance by modification or modification of sulfides.the heterostructure formed at the same time can not only effectively control the energy band of the oxide,but also accelerate the transfer of electrons at the interface,inhibit the recombination of photogenerated electron-hole pairs,and enhance the activity and stability of the photocatalytic reaction。

7 MOFs-derived carbon-sulfide, carbon-nitrogen-sulfide composites

the MOFs material can also be used as a precursor for preparing a carbon-based sulfide composite material,the MOFs is both a carbon source and a metal source,and the two components can be simultaneously retained by controlling the carbonization condition,To obtain MOFs-derived carbon-sulfide composites,the metal nodes of MOFs can be transformed into metal nanoparticles during high temperature treatment,while the organic ligands can be transformed into porous carbon materials[53]。 Graphene has good conductivity and excellent electron transfer ability,and loading on MOFs-derived sulfides can promote the separation of photogenerated charge carriers and the improvement of transport efficiency。
Graphite-like carbon nitride(g-C3N4)I s the most stable allotrope of carbon nitride with a graphite-like layered structure.As an inorganic nonmetallic semiconductor material with a band gap of∼2.7 eV,it has become a hot topic in the field of photocatalysis due to its simple preparation method,chemical stability,unique electronic structure,and response to visible light[54,55]。 As a result,the researchers mixed MOFs sulfide with g-C3N4to obtain carbon-nitrogen-based sulfide composite materials,which have greatly improved photocatalytic performance compared with single-component MOFs sulfide and g-C3N4,which is attributed to the energy level difference between the two components enhancing the absorption of visible light and promoting the separation of photogenerated charges 。
Multi-component MOFs are ideal platforms for the in situ growth of semiconductor nanoparticles,which can be simultaneously deposited on various carbon-rich scaffolds,and the enhanced interfacial interaction of particles grown in situ on carbonaceous supports can facilitate the transport of photogenerated carriers,thereby improving the photocatalytic degradation performance.Cao et al.Prepared a novel nitrogen-doped carbon-supported cadmium sulfide(CdS/NC-T)composite by a simple in-situ carbonization method using Cd-MOFs as the precursor(Fig.9)[56]。 the effect of calcination temperature on the catalytic performance of CdS/NC-T was further studied.the results showed that the optimal photocatalytic degradation efficiency of CdS/NC-500 for tetracycline(TC)was 83%(1 H)when the calcination temperature was 500℃.Due to the in situ growth of CdS nanoparticles on the carbonaceous support,the interfacial synergy is enhanced,resulting in the efficient generation and transport of photogenerated carriers。
图9 CdS/NC的制备过程示意图[56]

Fig. 9 Schematic illustration of the preparation procedure of CdS/NC[56]

MOFs-derived sulfides overcome the poor mechanical and chemical stability of pure MOFs,improve the stability and catalytic activity of catalysts,and inherit the porosity and multiple active centers of MOFs,which is conducive to the high turnover frequency of catalytic reactions and promote the smooth progress of photocatalytic reactions.Liu et al.Prepared the MoS2/CN composite catalyst by solvothermal reaction in one step from a mixture of Mo-MOF/g-C3N4[57]。 The effect of Mo-MOF addition on the catalytic performance was further investigated.The results showed that the best hydrogen production efficiency of MoS2/CN with 2 mg Mo-MOF addition was 1695.76μmol·g-1(4 h)under visible light.Under visible light,CN is excited to generate electrons and holes,and TEOA can react with the photogenerated holes of CN to inhibit electron-hole recombination,while the MoS2co-catalyst loaded on the surface of CN accelerates the transmission of photogenerated electrons,and the photocatalytic hydrogen evolution activity is greatly improved 。
MOFs derivatives are considered as potential high-performance co-catalysts because of their high specific surface area and high electrical conductivity,and ion exchange can simultaneously perform facile and effective structural and compositional transformations,and can avoid framework collapse during the conventional pyrolysis synthesis of MOFs materials.Chen et al.Prepared flower-like amorphous CoSx-C/N assembled by C/N-rich two-dimensional(2D)nanosheets by photoinduced anion exchange using ZIF-67 as a sacrificial template,and loaded it on a one-dimensional(1D)Cd0.5Zn0.5S(CZS)catalyst to form a unique 2D@1D composite photocatalyst with a high and low dimensional cross structure CoSx-C/Ny@CZS[58]。 Further study on the effect of different CoSx-C/N promoter content on the catalyst performance showed that the best hydrogen evolution activity of CoSx-C/N2@CZS with 3%CoSx-C/N promoter under visible light was 18.57 mmol·h-1·g-1,and the AQY reached 21.05%.The catalytic reaction mechanism shows that the photogenerated electrons are transferred to the two-dimensional catalytic active center CoSxthrough the Co-S-C/N charge channel for hydrogen evolution,while the photogenerated holes are left on the one-dimensional light absorption center CZS,which is eliminated by the sacrificial agent 。
The formation of heterostructure and the addition of rGO can promote the separation of photogenerated carriers and increase the transport rate,thus promoting the effective photocatalytic reaction.Si et al.Used ZIF-8 as precursor and TAA as sulfur source to react with g-C3N4nanosheets to synthesize g-C3N4/ZnS heterojunction[59]。 The effect of different weight ratios on the catalytic performance was further studied.The results showed that g-C3N4/ZnS-8∶1 had the best degradation effect on MO,and the degradation efficiency was 74.40%(160 min).The heterojunction formed by g-C3N4,ZnS enhances the photocatalytic degradation activity,and the flat surface of ZnS provides a close contact interface with g-C3N4,through which the photogenerated electron-hole pairs are effectively transferred and separated 。
Xu et al.Prepared Cu0.5Zn0.5In2S4quaternary hollow materials using CuZn-ZIF@MIL-68(In)layered MOFs as templates[60]。 Highly dispersed g-C3N4-rGO 2D-2D nanosheets were ingeniously inserted into the hollow tube wall to form Cu0.5Zn0.5In2S4-rGO-g-C3N4heterojunction.The effect of rGO addition on the catalytic performance was further investigated,and the results showed that the Cu0.5Zn0.5In2S4-rGO-g-C3N4with 0.5 wt%rGO exhibited the best hydrogen evolution rate(11.60 mmol·h-1·g-1)under visible light.The heterostructure formed by Cu0.5Zn0.5In2S4-rGO-g-C3N4and the high conductivity of rGO promote the separation of charge carriers and improve the transport efficiency 。
MOFs with permanent porosity can usually synthesize PCMs(porous carbon materials)with appropriate surface area and pore volume,which can promote the electron transfer rate by building the synergy between molecules and frameworks,molecules and molecules,thereby enhancing the photocatalytic activity.Choi et al.Successfully prepared In6S7NPs(multifunctional metal-derived nanoparticles)intercalated functional PCMs with S and N co-dopants by simple one-pot carbonization using In-MOF as a precursor[61]。 The effect of different preparation temperatures on the catalytic performance of PCM was further studied.The results showed that PCM-900(SBET=448 m2·g−1)prepared at 900°C exhibited the best photocatalytic activity with 88%MO degradation(160 min).Photocatalytically active semiconductor indium sulfide NPs with small band gap,Lewis basic S and N co-doped in carbon matrix,promote the interaction between CO2molecules and carbon framework 。
By changing the intrinsic activity of the active center,the ternary heterogeneous metal compound prepared by doping an element in the binary matrix can obtain higher photocatalytic activity.Qi et al.Prepared g-C3N4/C@Ni3S4/Ni2P by in situ sulfidation and phosphating of g-C3N4/Ni-MOF[62]。 The effect of phosphating time on the catalytic performance was further studied.The results show that the best hydrogen evolution performance of g-C3N4/C@Ni3S4/Ni2P under visible light is 14.49 mmol·h-1·g-1when the phosphating time is 30 min.The electronic interaction between Ni2P and Ni3S4,which synergistically increases the electron transfer rate,and the staggered band alignment of excited state EY,g-C3N4,Ni3S4,and Ni2P,improve the photocatalytic hydrogen evolution activity 。
MOFs and graphene-based materials can integrate the advantages of a single component,and then play a role in improving stability,modifying the structure,expanding the specific surface area,reducing aggregation,enhancing dispersion and improving catalytic activity.Yusuf et al.Synthesized a series of bimetallic MOFs using Cu and Ni as metal centers and carboxylate-rich pyromellitic acid(H4BTEC)as ligands by a facile method[63]。 Subsequently,mixed core-shell nanostructures of bimetallic Cu,Ni sulfides encapsulated on porous C were prepared from MOFs derivatives,and the MOF(Cu:Ni-BTEC/GO)was directly carbonized and sulfurized to prepare bimetallic sulfide Cu2S:NiS2@C/rGO.Cu2S:NiS2@C/rGO promoted phenylboronic acid and imidazole photocatalytic C-N coupling was applied to various substrates with conversion and selectivity greater than 90%.This indicates that Cu2S:NiS2@C/rGO possesses significant functional-group selective photocatalytic activity under mild conditions.The synergistic effect of non-noble metal Cu and Ni in the multifunctional structure of bimetallic sulfides enhances the photocatalytic activity of N-derivative compounds synthesized by oxidative coupling reaction 。
the MOFs-derived carbon-sulfide and carbon-nitrogen-sulfide composite materials Combine the advantages of each single component and retain the properties of high porosity,high specific surface area and multiple active sites of MOFs materials.combine that advantages of good electrical conductivity of carbon-based,visible light response of carbon-nitrogen base materials and stable chemical property,the problems of high recombination rate of photogenerated electron-hole pairs,low quantum yield and poor cycle stability exist in the photocatalytic reaction process are improved。

8 Conclusion and outlook

In this paper,the preparation and structure of MOFs-derived sulfides and their composites,as well as their applications in the field of photocatalysis,such as hydrogen evolution by hydrolysis,carbon dioxide reduction,and sewage treatment,are reviewed.MOFs-derived monometallic sulfides have better potential for photocatalytic degradation reactions,and MOFs-derived multi-component metal sulfides have more advantages for photocatalytic hydrogen evolution from water and CO2reduction,such as Ni-MOFs derived multi-component metal sulfides,which have the best hydrogen evolution rate,but there are few reports on photocatalytic CO2reduction.As a new type of photocatalytic material,sulfides derived from MOFs have many satisfactory advantages:(1)sulfides derived from MOFs retain the original structural characteristics of parent MOFs,with large surface area,dispersed nano-sized subunits and abundant active sites;(2)solving the problem of material stability of the parent MOFs in a high-temperature and harsh chemical environment;(3)narrower band gap and higher utilization rate of visible light;(4)Having a porous nature may provide an additional pathway for the migration of photoexcited electrons,thereby facilitating charge carrier separation.Although good results have been achieved in recent years,it should be recognized that the current research is still in the initial stage of laboratory research,and the application of MOFs-derived sulfides in the field of photocatalysis mainly has the following problems:(1)Some MOFs-derived sulfides materials have general or poor catalytic performance and still need to be modified;(2)The effect of the size and shape of MOFs-derived metal sulfides on the photocatalytic performance of composites is still not well studied;(3)The types of MOFs used in this field are generally limited to MIL-68,ZIF-8,ZIF-67,MOF-5 and MOF-74,and other MOFs with excellent photocatalytic activity still need to be expanded;(4)The effect of electron donors on the photocatalytic activity of MOFs-derived sulfide composites is still insufficient,and the use of sacrificial electron donors is generally limited to TEOA,lactic acid,methanol,and Na2S-Na2SO3;(5)Some MOFs-derived metal sulfides have poor cycle stability,such as Co-MOFs-derived multi-component metal sulfides,which need to add sacrificial agents to improve stability;(6)MOFs-derived metal sulfide supported photocatalysts have serious photocorrosion,which can be reduced by loading MOFs-derived sulfide semiconductors on other hole cocatalysts or layered oxide materials and mesoporous molecular sieves to form heterojunctions(Fig.10)and improve the stability of photocatalysts 。
图10 MOFs衍生金属硫化物稳定性提升策略图

Fig. 10 Stability enhancement strategy map for MOFs- derived metal sulfides

Although many advances have been made in this field,more research is still needed before these photocatalysts can be applied on an industrial scale.(1)On the premise that light harvesting is sufficient for the smooth progress of photocatalytic reaction,molecular control methods such as halogen doping,nitrogen and carbon co-modification,and vacancy construction can control the energy band and promote charge separation;(2)The introduction of other semiconductor materials combined with MOFs-derived sulfides to form various effective heterostructures is a widely studied method to effectively improve the carrier behavior and improve the catalyst cycle performance;(3)To further study the preparation of high-performance dye photosensitizers that can be tightly adsorbed on the surface of wide band gap semiconductors to improve the chemical reaction stability of photocatalysts under long-term illumination;(4)Strengthen the research on the immobilization and modification methods of photocatalyst.The metal carrier which is easy to be processed into a network can meet the requirements of carrier stability and large surface area,and also enable the attached photocatalyst to obtain more light and adapt to static or dynamic catalytic environment.(5)Further research and development of other low-cost,easily available and sustainable sacrificial electron donors;(6)In addition to the addition of sacrificial agents,partial oxidation can also reduce photocorrosion by consuming holes,and further research can combine photocatalytic hydrogen evolution with oxidation to produce H2and valuable substances at the same time;(7)Since the VB potential is not positive enough,MOFs-derived metal sulfides are often used as reductive photocatalysts for hydrogen production,CO2reduction and Cr(Ⅵ)reduction,and it is also important to apply MOFs-derived metal sulfides to photocatalytic oxidation.To this end,more efforts need to be put into the design improvement of MOFs-derived sulfides in the future to solve complex problems.Gratifyingly,the great potential of unique MOFs-derived sulfides provides a vast field for further development.Through unremitting efforts,it is expected to be implemented in practical production applications in the future 。
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