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

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Progress in Chemistry >

2024 , Vol. 36 >Issue 6: 939 - 948

DOI: https://doi.org/10.7536/PC231202

Review

Performance Improvement Strategy of Photocatalytic Ammonia Synthesis Catalyst

  • Lijun Guo , 1, * ,
  • Hong Yang 1 ,
  • Shengjuan Shao 1 ,
  • Yinqi Liu 1 ,
  • Jianxin Liu , 2, *
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  • 1 Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China
  • 2 College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
* E-mail: (Lijun Guo);
(Jianxin Liu)

Received date: 2023-12-14

  Revised date: 2024-02-12

  Online published: 2024-03-15

Supported by

National Natural Science Foundation of China(21978187)

Fundamental Research Program of Shanxi Province(202203021221058)

Scientific Technological Innovation Programs of Higher Education Institutions in Shanxi(2022L535)

Taiyuan Institute of Technology Scientific Research Initial Funding(2024KJ013)

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Abstract

Photocatalytic nitrogen fixation is driven by solar energy.N2and H2O are used to directly produce NH3at normal temperature and pressure,and the process has zero carbon emissions.It is one of the most promising artificial nitrogen fixation methods and has attracted wide attention from researchers in recent years.Limited by the difficult activation of N2,low utilization rate of photogenerated carrier and low utilization rate of sunlight,the ammonia production efficiency is still not high,so improving the ammonia production efficiency is the focus of research in the field of photocatalytic ammonia synthesis.Starting from the three important processes of N2adsorption activation,carrier separation and migration,and surface reaction,it is very promising to promote the activation and conversion of N2under mild conditions and produce NH3efficiently by reasonable modification of the catalyst.This paper mainly studied the modification of photocatalysts,summarized the influence of N2molecular adsorption and activation ability,photogenerated electron transfer ability and light utilization on the ammonia production efficiency,analyzed the research in recent years in these fields,and finally summarized the modification strategy of photocatalytic ammonia synthesis catalyst.

Contents

1 Introduction

2 Improving the adsorption and activation capacity of N2

2.1 Introducing defect site

2.2 Introducing metal site

3 Increased charge transfer capacity

3.1 Constructing the monometal mixed valence catalyst

3.2 Designing bimetallic site catalyst

3.3 Constructing multi-metal site catalyst

4 Improving light utilization

5 Conclusion and outlook

Key words： photocatalytic synthesis of ammonia; photocatalyst; active site; photogenic electron transfer ability; morphology control

Cite this article

Lijun Guo , Hong Yang , Shengjuan Shao , Yinqi Liu , Jianxin Liu . Performance Improvement Strategy of Photocatalytic Ammonia Synthesis Catalyst[J]. Progress in Chemistry, 2024 , 36(6) : 939 -948 . DOI: 10.7536/PC231202

1 Introduction

As one of the most important chemical products in the world,ammonia（NH3）can produce nitrogen fertilizer,is an efficient renewable fuel,and is a carbon-free energy storage intermediate.Because of these advantages and needs,NH3has been produced in large quantities.Photocatalytic nitrogen fixation is the production of ammonia by photocatalysis under environmental conditions,which has been widely studied because of its green and environmental protection.It uses sustainable energy as the driving force,water as the raw material of green hydrogen,and zero carbon emissions,which is the development direction of"green ammonia"in the future[1]。 Moreover,the solar energy that can be easily collected on the earth(about 5×1022J）per year)can fully meet the global energy demand[2]。 Through the photocatalyst,solar energy is directly collected and coupled to the catalytic reaction for chemical conversion,greatly reducing the energy demand[3,4]。 Since the pioneering report of photocatalytic N2reduction,researchers have explored a large number of photocatalytic materials in order to realize the development of this technology,but the efficiency of ammonia production is still unsatisfactory,and there is still a big gap from industrial application[5]。 Therefore,there is an urgent need to develop novel materials to improve the photocatalytic nitrogen fixation efficiency。
Photocatalytic nitrogen fixation using inexhaustible solar energy is a green and promising pathway for artificial nitrogen fixation.The process of photocatalytic N2reduction(NRR)can be divided into the following steps:(1)adsorption of nitrogen on semiconductor catalyst;(2)The semiconductor is illuminated to generate photogenerated electrons,which are excited to jump to the conduction band and leave holes in the valence band.The photogenerated electrons have strong reduction ability,and the photogenerated holes have strong oxidation ability,but most of the photogenerated electrons and holes will be ineffectively recombined;(3)At the same time,the unrecombined electrons and holes migrate to the surface of the catalyst and participate in the redox reaction on the surface.The H2O is oxidized by holes to release protons,and the N2adsorbed on the surface of the catalyst is reduced to NH3after combining photogenerated electrons and water protons.The photocatalytic nitrogen fixation process is shown in Fig.1 。
图1 光催化固氮原理示意图[6]

Fig. 1 Schematic diagram of photocatalytic nitrogen fixation[6]

In recent years,researchers have extensively studied the photocatalytic nitrogen fixation reaction through catalyst design and optimization.Bi-based materials(such as BiOCl,BiOBr,etc.),oxides,Mo-based materials,W-based materials and g-C3N4are the main photocatalysts for nitrogen fixation,which provide a good reference and inspiration for the improvement of photocatalytic nitrogen fixation efficiency,but the catalytic performance is still not ideal[7][8⇓~10][11⇓⇓⇓⇓~16][17⇓⇓⇓~21][22⇓~24][25⇓~27]。 The photocatalytic efficiency is largely limited by the difficulty of N2activation,the serious recombination of charge carriers and the low efficiency of light utilization,so it is very promising to promote the activation and conversion of N2under mild conditions and efficiently produce NH3by reasonably modifying the catalyst from the three important processes of N2adsorption and activation,charge carrier separation and migration,and surface reaction 。
in this paper,for the purpose of improving the photocatalytic nitrogen fixation activity,the strategies of constructing photocatalysts are summarized from the following three aspects:(1)constructing suitable active sites of catalysts to promote the adsorption and activation of nitrogen,so as to ensure the smooth progress of subsequent reactions;(2)the efficient separation and application of carriers are realized by strengthening the charge transfer ability,so that the carriers can effectively participate In the surface reaction,thereby improving the redox ability of the catalyst;and(3)improving the light absorption and utilization of the catalyst by adjusting the surface state of the catalyst。

2 Improvement of adsorption and activation ability of N2;

In the photocatalytic NRR system,the effective diffusion of nitrogen molecules on the active sites of the photocatalyst is the prerequisite for the subsequent N2chemisorption,and the adsorption and activation of N2are very difficult due to the high dissociation energy of N≡N bond up to 941 kJ·mol−1.Therefore,the main challenge of photocatalytic nitrogen fixation is the combination of catalyst and N2and the activation of strong N≡N bond[28,29]。 Therefore,the selection of appropriate active sites is essential for the adsorption and activation of N2,and it is an effective strategy to activate N2by constructing active sites to promote electron transfer to N2[30]。 active sites can be defined as catalyst surface sites,which interact with reactants or reaction intermediates to improve catalytic performance by influencing their adsorption,catalytic conversion,and desorption processes.the choice of the active site and the coordination/chemical environment adjustment of the active site play a crucial role in the enhancement of photocatalytic activity,which can reduce the activation energy barrier and thus promote the reaction[31]。 in the process of photocatalytic nitrogen fixation,the first prerequisite is to ensure that the surface of the catalyst has a good nitrogen adsorption capacity.nitrogen is activated and then reduced by hydrogenation.the more nitrogen and hydrogen participate in the reduction reaction,the higher the efficiency of photocatalytic nitrogen fixation will be.At present,the adsorption and activation sites of nitrogen in NRR system include vacancy,Fe metal site,Ru site,etc.,so researchers have done a lot of work around these active sites。

2.1 Introduced defect site

Anion vacancy plays an important role in the surface defect engineering of nitrogen-fixed photocatalysts.A feasible way to weaken N≡N is to create electron-rich active centers,while anion vacancy directly constructs electron-rich centers by reducing the number of adjacent coordinated non-metallic elements.When nitrogen is adsorbed,The transition metal(TM)binds to the N2throughσbond,and the unoccupied d orbital of TM accepts the electron density of the occupied p orbital of N,and then donates the valence electron of the occupied d orbital of TM toπ*of N,thus weakening the N—N bond.This strongπfeedback mechanism is beneficial to the activation of nitrogen[32,33]。 Fabrication of surface oxygen vacancies(OV or VO)or other anion vacancies(C,N,and S vacancies)is one of the effective strategies to obtain efficient photocatalytic nitrogen fixation.vacancies act as electron-rich centers.By introducing different vacancies into the catalyst,such as oxygen vacancies(OVs),nitrogen vacancies(NVs)and sulfur vacancies(SVs),the electronic structure,charge transport and surface adsorption capacity of the material can be effectively tuned.These vacancies are the main adsorption and active sites for heterogeneous catalysis,which can reduce the activation energy barrier and promote the catalytic reaction。
A large number of studies have found that oxygen vacancy is one of the important vacancies,which has a good effect on NRR reaction.oxygen vacancy and nitrogen have strong adsorption,which is conducive to the adsorption of nitrogen;the oxygen vacancy is also an electron capture site,which promotes the reduction of nitrogen by donating electrons[34⇓⇓⇓⇓~39]。 Wang et al.Designed MoO3−xnanowires containing asymmetric oxygen vacancy defects,and the defects introduced by OVs induced charge redistribution,which enhanced the adsorption and activation of N2[18]。 Meanwhile,the structure of the asymmetric defect facilitates the separation of photogenerated electron-hole pairs by charge redistribution on the nanoscale during photocatalytic nitrogen fixation.The zinc-doped Co3O4polyhedron prepared by Li et al.Has abundant oxygen vacancies on the surface,which not only provide active sites for nitrogen adsorption and activation,but also enhance the separation ability of the photocarrier and significantly improve the photocatalytic nitrogen fixation efficiency of the material[40]。 Sun et al.Constructed a VO-BiOBr/TiO2and comprehensively studied the effects of oxygen vacancies on the optical absorption,carrier lifetime,charge transfer,Photoelectrochemical properties and photoelectrocatalytic properties of the VO-BiOBr/TiO2,and found that the oxygen vacancies in the coordination unsaturated state lead to a defect level in the band gap of BiOBr.Resulting in enhanced optical absorption,while oxygen vacancies act as the capture centers of photogenerated electrons to activate the N2adsorbed on the surface of the catalyst,and the heterojunction between TiO2and VO-BiOBr reduces the interfacial transfer resistance,which is beneficial to the transfer of photogenerated carriers,thus improving the photoelectrocatalytic NRR activity[41]。
Sulfur vacancy is a common anionic vacancy,which can greatly contribute to the photoresponse characteristics[17,42,43]。 Sulfur vacancies play the role of the main reaction center in the semiconductor catalyst,which is beneficial to the separation of electron-hole pairs and the acceleration of carrier migration.The SV-1T-MoS2photocatalyst prepared by Tian et al.Has the advantages of more sulfur vacancies and 1 T phase,more active edge sites and good metal conductivity,higher nitrogen adsorption and activated sulfur vacancy content,enhanced light absorption intensity and absorption area,and better charge separation and transfer ability,which is beneficial to photocatalytic nitrogen fixation[44]。 The content of sulfur vacancies in the material also has a great effect on the photocatalytic conversion of N2.To explore its effect,Lan et al.Controlled the content of sulfur vacancies in the Bi2S3nanorods by changing the solvothermal reaction time,and the concentration of sulfur vacancies reached an optimal value in Bi2S3when the reaction time was 3 H[45]。 At this time,the N2capture ability,light response range,and nitrogen conversion efficiency of the Bi2S3-3 nanorods all reached the optimum level 。
Nitrogen vacancy is another common anion vacancy,and in addition to the same effect of the above two vacancies,NVs are more likely to trap N2atoms with similar structure and size as N atoms[32]。 In general,nitrogen-containing materials are more likely to produce nitrogen vacancies,such as CNT,g-C3N4,GCN,etc[46,47]。 Jiang et al.Designed and prepared NaYF4:Yb,Tm(NYF)modified carbon nitride nanotubes(NYF/NV-CNNTs)photocatalyst,and found that NVs greatly promoted the transfer of photogenerated electrons,and at the same time,it could enhance the active sites,enhance the adsorption of N2,and reduce the surface quenching effect of NYF NPs,thus promoting the energy migration within the heterojunction[48]。 the photocatalytic nitrogen fixation conditions of The above defective materials are shown in Table 1。
表1 Photocatalytic Nitrogen Fixation of Defect Materials

Table 1 Photocatalytic nitrogen fixation performance of defective materials

Photocatalyst Reaction medium Light source NH3 evolved Defect type Year Ref.
a-MoO3-x NWs Water 300 W xenon lamp 200.35 μmol·h-1·g-1 OVs 2023 18
Zn-Co3O4 Water 300 W xenon lamp
(λ ≥ 420 nm)		 96.8 μmol·h-1·g-1 OVs 2023 40
SV-1T-MoS2 Water+ Methanol 300 W xenon lamp
(AM 1.5G)		 8220.83 μmol·h-1·g-1 SVs 2020 44
Bi2S3 Water 300 W xenon lamp 51.04 μmol·L-1·h-1 SVs 2022 45
NYF/NV-CNNTs Water +
Sacrificial agent		 300 W xenon lamp
(λ ≥ 420 nm)		 1.72 mmol·L-1·g-1 NVs 2021 48

2.2 Introduced metal site

The introduction of metal sites with strongπfeedback mechanism is another strategy to enhance nitrogen activation.Nanomaterials adsorb N2on the surface to form TM-N bonds,which can better activate nitrogen.The binding strength of TM-N can be adjusted by optimizing TM elements.Therefore,it is feasible to introduce metal sites as activation sites to activate nitrogen[49,50]。
(1)metallic Fe
It has been shown that high photocatalytic nitrogen reduction activity and ammonia synthesis ability can be obtained by introducing transition metals into semiconductors to promote the cracking process of N≡N,in which Fe is recognized as an ideal N2reduction site[51⇓⇓~54]。 Iron plays a key role in both biological and artificial nitrogen fixation.The study of biological nitrogen fixation system shows that Fe is the preferential active site for N2binding and reduction in FeMo protease[55]。 In the industrial nitrogen fixation process,iron is also the main catalyst,and the key steps involve the chemisorption of N2on the Fe surface and the formation of Fe—N complex.Therefore,transition metal Fe is considered to be an important catalytic active site in industrial and biological nitrogen fixation[56]。 In the photocatalytic nitrogen fixation system,Fe has multiple advantages.First,Fe not only affects the crystal structure of the catalyst,but also helps to trap photogenerated electrons and holes and inhibit their recombination,and this electron-hole separation process can effectively improve the efficiency of photocatalytic nitrogen fixation[57]。 Secondly,because the N2molecule has lone pair electrons,and the empty d orbital of Fe can receive these lone pair electrons,in addition,the Fe atom has independent d electrons,which can contribute to the antibonding orbital,thus strengthening the Fe—N bond and breaking the N≡N bond.This enhancement of Fe—N bond is very important for effective capture and activation of N2,so iron-based materials have high photocatalytic nitrogen fixation activity,and there are a lot of studies in the field of photocatalytic nitrogen fixation 。
The theoretical calculation results of Azofra et al.Showed that in the Fe-MoS2system,the chemical adsorption capacity of N2molecules on the catalyst could be significantly improved by introducing Fe centers to form stronger interactions with N2molecules.This enhanced adsorption capacity helps to reduce the activation energy barrier of N2and promote the electron transfer from the catalyst to the N2molecule,thus realizing the activation of N2and promoting the improvement of nitrogen fixation performance[58]。 Shen et al.Prepared FeⅢdoped flower-like BiOCl with high active site exposure and good N2photofixation performance[57]。 FeⅢis not only the reaction center for N2activation,but also the"electron transfer bridge"in BiOCl to capture and migrate electrons to N2molecules.Zhao et al.Prepared an Fe-doped modified TiO2catalyst and studied its performance in photocatalytic nitrogen fixation[59]。 Fe doping can accelerate the transfer of electrons and holes,prevent recombination,and promote the adsorption and activation of N2in the photocatalytic nitrogen fixation process,and the photocatalytic activity of the catalyst is improved.Liu et al.Prepared Fe-doped BiOBr photocatalyst,and used BiOBr as the matrix to introduce Fe active sites to improve the nitrogen fixation efficiency[60]。 Fe is the active site for the adsorption and activation of N2,and the doping of Fe promotes the formation of more OVs.According to the theoretical calculation,it is found that the Fe atom connected by OVs will withdraw the photoexcited electrons from other atoms nearby,forming electron-rich Fe(Ⅱ).Excess electrons in the 3D orbital of Fe(Ⅱ)will be injected into theπN—N antibonding orbital of the adsorbed N2by electron feedback,which finally increases the nitrogen fixation efficiency by 8 times.Zhao et al.Prepared Fe-doped SrWO4nanoparticles and found that the intrinsic band gap of SrWO4was greatly reduced by Fe doping,which not only expanded the absorption range from ultraviolet to visible light,but also reduced the charge recombination,and Fe doping also introduced the FeⅡ/FeⅢredox pathway to the surface center of NRR,and finally improved the NRR efficiency[61]。 The nitrogen fixation conditions and yields of some Fe-doped literatures are summarized in Table 2。
表2 Photocatalytic nitrogen fixation of Fe-doped materials

Table 2 Iron-doped materials for photocatalytic N2fixation

Photocatalyst Reaction medium Light source NH3 evolved Year Ref.
Fe-BiOCl Water 300 W xenon lamp 30.00 μmol·L-1·h-1 2020 57
Fe-BiOBr Water 300 W xenon lamp
(λ≥ 420 nm)		 382.68 μmol-1·g-1·h-1 2020 60
Fe-SrWO4 Water 300 W xenon lamp 150.70 μmol·h-1·g-1 2020 61
Fe0.05-CN Water + Alcohol 250 W high voltage
sodium lamp		 5.40 mg·L-1·h-1·g-1 2017 62
Fe-MCNC Water + Methanol 65 W LED 1.88 μmol·h-1·g-1 2023 63
(2)metallic Ru
Ru is considered to be a second-generation catalyst for NH3synthesis.Because the N2reduction potential of Ru is lower than that of Fe,Ru atom can transfer electrons from its d-orbital to its antibonding orbital,which promotes the dissociative chemisorption of N2,thus accelerating the reaction[64]。 Compared with Fe,Ru is more conducive to the activation of N≡N,because it requires relatively mild reaction conditions,which is consistent with the photocatalytic environment,so Ru is considered to be a better catalytic active site for photocatalytic NH3synthesis than Fe[65,66][67,68]。 First,the Ru-loaded active site can significantly improve the photocatalytic activity.This is because the interaction between Ru and oxygen-containing carriers can construct Ru-O-M(M refers to other metals)sites[69⇓~71]。 At the same time,such interaction can promote the electron transfer to the adsorbed N2,further improving the photocatalytic nitrogen fixation efficiency.Secondly,Ru nanoparticles can produce photogenerated electrons under photoexcitation and can change the electronic structure around other metals,which makes Ru widely used in photocatalytic nitrogen fixation[72,73]。 In the field of photocatalytic nitrogen fixation,there have been many reports on the use of Ru loading to modify the catalyst to improve the photocatalytic activity and improve the reaction efficiency。
Liu et al.Distribute Ru single atoms on the（Ru1/2DAF）of amorphous iron oxide nanosheets,and the amorphous iron oxide can adjust the density of electronic States,reduce the energy barrier of electron transfer,and construct electronic channels through d(Ru)-d(Fe)coupling.Electrons are directed from the amorphous support to the Ru 4D orbital,which accelerates the enrichment of photogenerated electrons on the Ru active site,thereby promoting the adsorption and activation of N2,and ultimately improving the reaction activity.Fig.2a is a schematic diagram of photogenerated electrons of Ru1/2DAF[74]。 Ding et al.Constructed a Ru-MOF-74 system,and found that Ru did not replace Zn in MOF-74,but existed in the internal channel.The introduction of Ru promoted the adsorption of N2,prolonged the visible light response,promoted the separation of carriers,and effectively transferred carriers to the surface of the catalyst,thus improving the photocatalytic nitrogen fixation performance[75]。 Li et al.Designed Ru cluster-assisted III-nitride nanowire Ru@GaN for photocatalytic nitrogen fixation.Metal Ru and the substrate form an interface Schottky,so that electrons are transferred from III-nitride to Ru.Ru acts as an electron pool,reducing the activation barrier of the N2dissociation reaction.The schematic diagram of the Schottky barrier formed is shown in Figure 2b[76]。 Liu et al.Designed a single-atom Ru-decorated oxygen-vacancy rich TiO2nanosheet,and the experimental results confirmed that a single Ru site could promote the photoreduction of N2to generate NH3.Ru atoms weaken the hydrogen evolution,promote the absorption of N2,and improve the carrier separation,thus enhancing the N2photofixation,and its N2photoreduction mechanism is shown in Figure 2C[77]。 The Ru/W18O49designed by Li et al.Constructed asymmetric active sites,Ru-O-W centers can be used as N2adsorption sites,which can better promote the transfer of electrons to the adsorbed N2,and the plasmon resonance effect between Ru and oxygen vacancies provides enough electrons for nitrogen activation,both of which work together to achieve the purpose of improving photocatalytic nitrogen fixation activity[30]。 the nitrogen fixation conditions and yields of The above references are summarized in Table 3。
图2 (a) Ru1/2DAF的光生电子转移示意图[74]; (b) n型GaN NWs与金属Ru团簇形成肖特基势垒的示意图[76]; (c) 含氧空位的Ru负载TiO2纳米片上N2光还原机理图[77]

Fig. 2 (a) Schematic diagram of photogenerated electron transfer in Ru1/2DAF[74]. (b) Schematic diagram for the formation of the Schottky barrier between n-type GaN NWs and metallic Ru clusters[76]. (c) Mechanistic diagram of N2 photoreduction over single Ru site loaded TiO2 nanosheets with oxygen vacancies[77]

表3 Photocatalytic Nitrogen Fixation Performance of Ru Supported Material

Table 3 Photocatalytic nitrogen fixation of Ru supported materials

Photocatalyst Reaction medium Light source NH3 evolved Year Ref.
Ru/W18O49 Water 300 W xenon lamp 44.30 μmol·g-1·h-1 2023 30
Ru1/2DAF Water 300 W xenon lamp 213.00 μmol·g-1·h-1 2022 74
Ru-MOF-74 Water 300 W xenon lamp
(λ ≥ 420 nm)		 70.90 μmol·g-1·h-1 2022 75
Ru@GaN Hydrogen +
Nitrogen		 UV lamp 290-380 nm 2400.00 μmol·g-1·h-1 2017 76
Ru-TiO2 Water + Alcohol 300 W xenon lamp 56.30 μg·h-1·g-1 2019 77

3 Improvement of charge transfer capability

Another goal of catalyst modification is to improve the charge transfer ability to promote the effective separation of electron-hole,thereby accelerating the redox reaction and ultimately improving the efficiency of photocatalytic nitrogen fixation.the construction of a catalyst with charge transfer ability can be accomplished in the following way。

3.1 Construction of monometallic mixed-valence catalyst

In the catalytic site,the valence state of the metal active center determines the electrophilicity and coordination ability of the catalyst,thus affecting its interaction with reactants and reactivity[78]。 the mixed-valence metal center usually has better catalytic ability because it can perform reversible redox reactions in the reaction,providing more flexible electron transfer ability,which enables the metal center to participate in photogenerated charge transfer and catalytic reactions more effectively[79][80]。
It was found that the Mo valence in nitrogenase is the key to the activity of FeMo factor,which completes the nitrogen fixation process through Mo3+and Mo6+cycle.Inspired by this,Li et al.Constructed a Mo valence-changing catalyst MoO2+xto obtain Mo6+through valence control,which can inhibit hydrogen evolution and thus facilitate nitrogen activation(Fig.3 )[81]。 Yuan et al.Used mixed-valence cobalt to modulate tungsten trioxide nanorod arrays to improve the photocatalytic nitrogen fixation performance(Fig.4)[82]。
图3 原始MoO2 (a)和表面富集Mo6+的MoO2+x (b)上的NRR和HER示意图[81]

Fig. 3 The schematic of NRR and HER on (a) pristine MoO2 and (b) MoO2+x enriched with surface Mo6+[81]

图4 富OVs的WO3·0.5H2O光催化固氮过程的反应路径[82]

Fig. 4 Possible reaction path during the photocatalytic N2 fixation of rich-OVs in WO3·0.5H2O[82]

The formation of low-valent cobalt was used to create oxygen vacancies(OVs)to improve the catalytic activity by constructing a Co2+/Co3+cycle.Moreover,the Co2+/Co3+cycle is generated by light excitation and can be restored after illumination.In the photocatalytic nitrogen fixation reaction,the metal active center adsorbs and activates nitrogen by absorbing light energy,and then a series of redox reactions occur,and ammonia is converted into available ammonia.Under light conditions,the redox cycle of metal active centers can switch between different oxidation States and reduction States.Therefore,accelerating the variable valence cycle of metal active sites can improve the redox ability of photocatalytic nitrogen fixation,and the construction of catalysts with high reduction/oxidation ratio is the prerequisite for improving the redox reaction 。
Iron metal is a typical mixed-valence metal.In the nitrogenase of biological nitrogen fixation,the iron of FeMo factor exists in the form of mixed valence of FeⅡand FeⅢ.FeⅡis the adsorption and activation site of nitrogen,and FeⅢdoes not participate in the reduction process of nitrogen,but ensures the stability of enzyme cluster structure[83][84]。 The high activity of Fe1-xO based catalysts in industrial ammonia synthesis is due to the coexistence of FeⅡand FeⅢ[85]。 Either biological nitrogen fixation or industrial nitrogen fixation is a mixed valence system of FeⅡand FeⅢ,and its valence can be reversibly converted between FeⅢand FeⅡ.Because FeⅡhas a stronger interaction with unsaturated molecules,it acts as an adsorption and activation site for nitrogen,and increasing the proportion of FeⅡis beneficial to the nitrogen fixation reaction[86]。 Jiang et al.Designed a MIL-53(FeⅡ/FeⅢ)photocatalyst for photocatalytic nitrogen fixation research,through a one-step solvothermal method,the FeⅢin MIL-53(FeⅡ/FeⅢ)was partially reduced to FeⅡin situ by ethylene glycol(EG).Photocatalysts with mixed-valence metal clusters of FeⅡand FeⅢwere constructed,and it was experimentally confirmed that the FeⅡ/FeⅢratio is a key parameter affecting the catalytic activity and framework stability of MIL-53(FeⅡ/FeⅢ ))[87]。

3.2 Design of bimetallic site catalyst

In photocatalytic systems,the charge transfer rate determines the ability for efficient charge separation,which affects the photocatalytic activity of the catalyst.The design of bimetallic active sites with different electron acceptances in photocatalysts can simultaneously couple electron acceptance and feedback processes to accelerate charge transfer,thereby promoting N2activation[88]。 Moreover,due to the interaction between different metals,such as synergistic effect,the spatial structure and electronic structure of clusters will change,thus showing different catalytic activities[89]。 Therefore,the design of bimetallic site catalysts provides a possible environment for the nitrogen fixation reaction path[90]。
Inspired by the"FeMo cofactor"of biological nitrification enzymes,Li et al.Constructed a novel biomimetic Fe/Mo bimetallic photocatalyst,which can effectively promote the separation and transport of photogenerated carriers through multi-electron redox reactions,prolonging the carrier lifetime by 2.8 times and increasing the nitrogen fixation activity by 4.8 times[91]。 Ni et al.Constructed a photocatalyst with CeF3:Yb3+,Er3+/Fe-ATP heterostructure for full-spectrum nitrogen fixation,and the fluorine vacancy(FV)in CeF3and Fe in ATP formed double active sites,which promoted the activation of nitrogen molecules and effectively reduced the activation energy of inert N2in the photocatalytic nitrogen fixation reaction[92]。 the active nitrogen is transferred to the Fe-ATP surface to form the Fe—N=N bond,which makes it easier to hydrogenate.After the participation of photogenerated electrons,Fe—N=N becomes a new reaction center,while FV acts as a charge mediator to establish an indirect Z-shaped structure,which promotes the separation of charges and ultimately leads to higher nitrogen fixation activity.Scholten et al.Constructed a sustainable catalytic system of bimetallic RuPd nanoparticles supported on graphitic carbon nitride for photocatalytic nitrogen fixation.Ru weakens the N≡N bond and Pd bonds H.the favorable synergistic effect between the two metals leads to its unique catalytic performance[93]。 the principle of nitrogen fixation is shown in Fig.5.Table 4 lists the applications of some bimetallic site materials in the field of photocatalytic nitrogen fixation。
图5 RuPd NPs/C3N4光催化固氮原理图[93]

Fig. 5 Schematic diagram of RuPd NPs/C3N4 photocatalytic nitrogen fixation[93]

表4 Photocatalytic Nitrogen Fixation Performance of Bimetallic Site Material

Table 4 Bimetallic site materials for photocatalytic N2fixation

Photocatalyst Reaction medium Light source NH3 evolved Year Ref.
Fe/Mo-BMWO Water 300 W xenon lamp
(λ ≥ 420 nm)		 218.93 μmol·h-1·g-1 2022 91
CeF3:Yb3+, Er3+/Fe-ATP Water 300 W xenon lamp 253.60 μmol·h-1·g-1 2022 92
RuPd/C3N4 Water + Alcohol 300 W xenon lamp 1389.84 μmol·h-1·g-1 2021 93
Ru-SA/ HxMoO3−y Hydrogen + Nitrogen 300 W xenon lamp
(λ≥ 420 nm)		 4.00 mmol·h-1·g-1 2022 94
RuO+Co/CoO Water 300 W xenon lamp
(λ≥ 400 nm)		 306.00 μmol·h-1·g-1 2022 95
Inspired by the above studies,it is a feasible idea to construct bimetallic systems with different functional roles by combining the hydrogenation mechanism of photocatalytic nitrogen fixation.the charge flow between bimetals is used to accelerate the redox reaction,and different metals complete the nitrogen activation and hydrogenation processes respectively in the nitrogen fixation process,thus completing the whole reaction process synergistically and further improving the catalytic activity。

3.3 Construction of multi-metal site catalyst

Compared with traditional single-metal photocatalysts,multi-metal-site photocatalysts have unique advantages and potential applications in catalytic performance and reaction mechanism.It can take advantage of the characteristics of different metals,such as different electronic structures,band structures and coordination characteristics,to achieve more abundant and diverse reaction paths and reaction mechanisms.This multi-metal synergism can improve the charge transfer ability,redox ability and catalytic activity of the catalyst,thereby enhancing the efficiency and selectivity of the photocatalytic reaction.Ma et al.Improved the photocatalytic hydrogen evolution performance over(Ru/WC)/CdS catalyst by adjusting the transfer path of photoexcited electrons[96]。 Ru is the catalytic active center for hydrogen generation because of its fast electron transfer,WC has a large specific capacitance,and CdS collects and stores photogenerated electrons.It is clear that the photoexcited electron transfer path is from CdS to WC and Ru in turn.Zhang's team constructed K/Ru/TiO2-xHxmulti-metal-site nitrogen fixation catalyst to achieve efficient solar ammonia synthesis,and both K and electron-rich carrier TiO2-xHxrich in oxygen vacancies(OVs)can adjust the electronic structure of Ru to effectively activate nitrogen[97]。 In addition,the interfacial structure of TiO2-xHxaccepts hydrogen atoms from Ru,which makes the catalyst surface more active.The interface also minimizes the problem of hydrogen poisoning while nitrogen is fixed.The TiO2-xHxat the interface accepts H atoms from Ru and passes them on to the Ru-activated N2,eventually forming Ti-NHx 。

4 Improve light utilization

morphology control has a wide range of applicability in the regulation of photocatalytic performance.By rationally designing the Morphology of photocatalysts,light scattering centers are introduced on the surface of photocatalysts to achieve efficient light absorption,charge separation and transport,thus accelerating the surface reaction and ultimately improving the photocatalytic activity[98][99⇓~101]。 It is found that the rough surface has a higher light utilization efficiency than the smooth surface,because the rough surface can provide more scattering centers[102]。 in addition,the hollow structure or core-shell structure is also an effective way to improve the light utilization efficiency.These structures can be used as good light scattering centers.After multiple reflections and refractions In the process of light propagation,the interaction between light and materials is increased,and more active sites are excited,which improves the light utilization efficiency and enhances the photocatalytic activity[103,104]。
Zhu et al.Designed a core-shell structure of SiO2@ZnS/CuSxcatalyst,and the incident light was reflected and scattered by the white SiO2core after passing through the ZnS/CuSxshell,and then collected by the ZnS/CuSx[105]。 Fig.6a is a light scattering schematic diagram of a core-shell SiO2@ZnS/CuSx.Zaine et al.Improved the light scattering efficiency of photoelectrode DSSCs by optimizing the core-shell structure of SiO2-TiO2[106]。 Bai et al.Designed a C/CdS@ZnIn2S4core-shell photocatalyst for CO2reduction,and attributed its excellent photocatalytic performance to hollow carbon.First,multiple light reflection and scattering improved light harvesting,promoted charge separation,and facilitated electron collection.Secondly,the large surface area provides more highly active and selective sites for targeting the reduction reaction,the porous shell spatially separates the reduction and oxidation half-reactions,and protects CdS from photocorrosion,and the core-shell structure extends the light response range to longer wavelengths,and achieves the effect of spatial separation through electrons and holes on different components[107]。 Fig.6B is a schematic diagram of light utilization of the C/CdS@ZnIn2S4core-shell structure photocatalyst 。
图6 (a) 核壳SiO2@ZnS/CuSx的光散射原理图[105]. (b) C/CdS@ZnIn2S光催化机理示意图[107]

Fig. 6 (a) The schematic proposal of light scattering on core-shell SiO2@ZnS/CuSx[105]. (b) Schematic illustration of the photocatalytic mechanism in C/CdS@ZnIn2S[107]

5 Conclusion and prospect

Photocatalytic nitrogen fixation is one of the most promising artificial nitrogen fixation methods,which uses solar energy as the driving force,uses N2and H2O to produce NH3directly at normal temperature and pressure,and has zero carbon emissions.Photocatalytic nitrogen fixation has made some progress,but its performance is far from the actual industrial production needs,so improving its efficiency has been the direction of researchers.In this paper,the strategies to improve the efficiency of photocatalytic nitrogen fixation are discussed and summarized in detail from the perspective of photocatalyst modification and the reaction process of photocatalytic nitrogen fixation.In order to further improve the efficiency of photocatalytic nitrogen fixation,the design ideas of photocatalysts can be further studied from the following aspects.Adsorption and activation ability of（1）N2The adsorption and activation of：N2on the catalyst is the first step of nitrogen fixation,and the construction of active sites with high adsorption and activation ability of N2is an effective strategy to improve the efficiency of nitrogen fixation.Combined with advanced characterization techniques and theoretical research methods,more accurate and efficient active sites are selected to activate N2to the greatest extent,thus improving the efficiency of N2reduction.(2)Charge transfer ability:improve the migration ability of photogenerated electrons,so that they can directionally and rapidly migrate to the surface of the catalyst,and efficiently reduce the N2.A variety of in-situ characterization technologies are constructed to monitor and accurately grasp the migration path of photogenerated electrons in real time,so as to improve the utilization rate of photogenerated electrons.(3)Sunlight utilization rate:Different strategies can be used to improve the utilization rate of sunlight,including designing the surface structure of the catalyst and regulating the surface morphology 。
In addition to improving the efficiency of photocatalyst,we can improve the whole process of photocatalytic nitrogen fixation,design a systematic and standardized photocatalytic nitrogen fixation system to simulate the industrial production process,and comprehensively evaluate and optimize the efficiency of nitrogen fixation。

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