English

• 0.   Introduction

  Over-reliance on fossil fuels has driven a persistent increase in global CO₂ levels, amplifying the greenhouse effect and deepening ecological challenges^[1-2]. Consequently, the utilization of CO₂ as a resource has emerged as a pivotal challenge in achieving carbon neutrality goals. CO₂, serving as a C1 resource, can be catalytically transformed into value-added chemicals such as methane, methanol, and cyclic carbonates^[3-4]. Although the conversion of CO₂ into cyclic carbonates achieves 100% atom utilization^[5], traditional synthesis methods require high-temperature and high-pressure conditions, presenting significant challenges including excessive energy consumption and limited sustainability^[6].

  To overcome these constraints, photocatalytic technology utilizes solar energy to facilitate the moderate cycloaddition of CO₂ with epoxides^[7]. Upon photoexcitation with energy exceeding the bandgap (E_g), photoinduced electron-hole pairs are generated in the semiconductor, which would migrate to the surface active sites and undergo further reactions^[8].

  This manuscript focuses on the analysis of MOF-based photocatalysts for the CO₂ cycloaddition reaction, with a particular emphasis on mechanistic insights and strategies for performance enhancement. The study elucidates the fundamental pathways governing radical-anion formation and epoxide activation, substantiated by empirical evidence. Furthermore, we examine three pivotal approaches, including ligand engineering, composite construction, and dopant incorporation, to address current limitations. This research endeavors to provide a critical overview of MOFs in the photocatalytic synthesis of cyclic carbonates, encompassing their structural characteristics, photocatalytic mechanisms, current challenges, and prospective developments.

  1.   Mechanism of photocatalytic CO₂ cycloaddition

  The excitation and separation of photogenerated carriers and their cooperative activation process with the reactants form the basis of the fundamental mechanism of the photocatalytic CO₂ cycloaddition reaction. Current research focuses on the following two types of pathways:

  (1) Radical-anion pathway: the electrons (e^-) generated by photoexcitation migrate to the surface active sites through the directional transfer channel from MOFs′ ligands to metal clusters. The photoelectrons reduce CO₂ to obtain ·CO₂^- radical anion, which then interacts with epoxide activated by the Lewis acid sites to produce cyclic carbonate^[9] (Fig. 1a). The mechanistic pathway is exemplified through Fe-FcDC, wherein the organic ligand (1, 1′-ferrocenedicarboxylic acid, H₂FcDC) facilitates photon absorption and charge carrier generation. The photogenerated electrons undergo directional migration through the synergistic interplay between FeO₆ clusters and ferrocenyl moieties, ultimately reaching surface active sites where they facilitate CO₂ activation to form ·CO₂^-, thus promoting the desired transformation^[10].

  Figure 1

  

  Figure 1.  Two mechanism diagrams of the photocatalytic CO₂ cycloaddition reaction: (a) radical-anion pathway and (b) epoxide-activation pathway

  下载: 全尺寸图片 幻灯片

  (2) Epoxide-activation pathway: alternatively, a negatively charged intermediate is created when the photoelectrons directly interact with the epoxide. The co-catalyst, most commonly tetrabutylammonium bromide (TBAB), facilitates Br^--mediated nucleophilic ring opening, subsequent CO₂ insertion, and ring closure to afford cyclic carbonate^[11] (Fig. 1b). Other nucleophilic salts, such as tetrabutylammonium iodide (TBAI) or potassium iodide (KI), can also be employed. However, their efficacy may vary depending on the catalytic system^[5]. A representative illustration is demonstrated by PB-modified WO_3-x, wherein photoexcitation induces electron capture at oxygen vacancy sites. These trapped electrons subsequently interact with epoxy functionalities, generating highly reactive anionic intermediates that undergo successive transformations to yield the desired products^[12].

  2.   Enhancement of MOFs′ photocatalytic properties

  MOFs have emerged as promising photocatalysts for CO₂ conversion into cyclic carbonates, owing to their unique structural advantages over conventional catalysts^[13]. Their tunable pore architectures and abundant Lewis acid-base sites enable synergistic activation of both CO₂ and epoxides, effectively lowering the energy barrier for ring-opening reactions. The photocatalytic mechanism in MOFs originates from light absorption by conjugated organic ligands, which generates excitons that undergo directional charge transfer to metal clusters through well-defined coordination pathways^[14-15]. However, the practical application of MOF-based photocatalysts faces two fundamental challenges: narrow photo-response range and inefficient charge carrier separation^[16]. This review aims to provide a comprehensive overview of recent progress in MOF-based photocatalytic systems for CO₂ cycloaddition, systematically elucidating the structure-activity relationship in MOF-based photocatalysts, with particular focus on innovative design strategies to address these limitations, including extending the photo-response range through ligand engineering and sensitization, and enhancing charge separation efficiency via structural modifications and heterojunction construction. By comprehensively analyzing these approaches, we establish guidelines for developing high-performance MOF-based photocatalysts for sustainable CO₂ utilization.

  Analysis of the performance data in Table 1 reveals several key trends. Significant variation in yield is observed, ranging from below 0.2 mmol·g^-1·h^-1 to nearly 298 mmol·g^-1·h^-1, highlighting the profound impact of catalyst design. Factors influencing performance include the nature of the MOF (metal nodes, organic ligands, presence of dopants), the formation of composites or heterojunctions, light source intensity and wavelength, reaction time, and the specific epoxide substrate used (e.g., styrene oxide often requires longer times than epichlorohydrin). Notably, strategies such as incorporating redox-active ligands (e.g., Fe-FcDC^[10]), heteroatom doping (e.g., UiO-67-B^[42]), and constructing advanced composites (e.g., PMo₁₂@Zr-Fc^[41]) have successfully yielded catalysts exhibiting high productivity (> 40 mmol·g^-1·h^-1), demonstrating the effectiveness of the optimization approaches discussed in this review.

  Table 1

  

  Table 1.  Performance comparison of MOFs for photocatalytic CO₂ cycloaddition

  下载: 导出CSV

  Catalyst	Light source	Time /h	Reaction substrate	Conversion /%	Yield /(mmol·g-1·h-1)	Regulatory strategy	Ref.
  Fe-FcDC	300 W xenon lamp	4	Epichlorohydrin	7	44	Ligand engineering	[10]
  Co-PMOF 3	300 W xenon lamp	6	Epichlorohydrin	> 99	61	Ligand engineering	[17]
  MOF-997	300 W xenon lamp	24	Styrene oxide	> 99	2	Ligand engineering	[18]
  Th-IHEP-5	45 W fluorescent light	48	Styrene oxide	71	0.6	Ligand engineering	[19]
  Zr-TTF-L1	300 W xenon lamp	8	Propylene oxide	45	14	Ligand engineering	[20]
  MOF 1 (Mn)	LED 18×3W	24	Epichlorohydrin	100	17	Ligand engineering	[21]
  Fe-DBP(Co)	1000 W xenon lamp	12	Epichlorohydrin	97	103	Ligand engineering	[22]
  FeTPyP	300 W xenon lamp	5	Styrene oxide	30	106	Ligand engineering	[23]
  Bi-HHTP	300 W xenon lamp	4	Styrene oxide	34	112	Ligand engineering	[24]
  Mg-MOF-74	400 mW·cm-2	12	1-Bromo-2,3-epoxypropane	97	5	Ligand engineering	[25]
  UAEU-50	400 W halogen lamp	24	Styrene oxide	90	6	Ligand engineering	[26]
  Co-HOF	400 W halogen lamp	24	Styrene oxide	> 99	6	Ligand engineering	[27]
  NH2-MIL-68	300 W xenon lamp	12	Styrene oxide	94	56	Ligand engineering	[28]
  Ti-H2TPDC	8 W LED light	4	Epichlorohydrin	94	59	Ligand engineering	[29]
  PB-modified WO3-x	300 W xenon lamp	8	Styrene oxide	94	171	Composite construction	[12]
  W18O49/NH2-UiO-66	300 W xenon lamp	4	Styrene oxide	82	58	Composite construction	[30]
  FeNbO4/NH2-MIL-125(Ti)	500 W halogen lamp	72	Propylene oxide	52	0.2	Composite construction	[31]
  MIL-125@ZIF-67	3 W blue LED	36	1-Bromo-2,3-epoxypropane	99	0.3	Composite construction	[32]
  Co2N0.67@ZIF-67	350 mW·cm-2	3	Epichlorohydrin	95	3	Composite construction	[33]
  Zn20Fe1-ZIF/MXene	350 mW·cm-2	6	Epichlorohydrin	96	16	Composite construction	[34]
  CMS@MIL-88-NH2	300 W xenon lamp	6	1, 2-Epoxybutane	72	24	Composite construction	[35]
  Zn SA-NC	300 mW·cm-2	16	Epichlorohydrin	99	0.5	Composite construction	[36]
  CoNHPC/TM-8	350 mW·cm-2	12	Styrene oxide	99	8	Composite construction	[37]
  CuS@HKUST-1	Blue light	18	2-Chloromethyl-oxriane	98	11	Composite construction	[38]
  Ag0.1/NWU-Cd3a	300 W xenon lamp	6	Styrene oxide	94	22	Composite construction	[39]
  Zn-N-HOPCPs	350 mW·cm-2	10	Propylene oxide	95	29	Composite construction	[40]
  PMo12@Zr-Fc	500 mW·cm-2	8	Epichlorohydrin	96	298	Composite construction	[41]
  UiO-67-B	300 W xenon lamp	6	Propylene epoxide	6	45	Dopant incorporation	[42]
  Bi-PCN-224	300 W xenon lamp	6	Propylene epoxide	99	5	Dopant incorporation	[43]
  Tb-DBP(Co)	300 W xenon lamp	10	Epichlorohydrin	> 99	127	Dopant incorporation	[44]
  SNNU-97-InV	300 W xenon lamp	24	2-Bromooxirane	97	14	Dopant incorporation	[45]
  Zn-UiO-bpydc	300 W xenon lamp	9	Propylene oxide	75	0.3	Dopant incorporation	[46]
  IHEP-9	45 W compact fluorescent lamp	12	Styrene oxide	99	2	Dopant incorporation	[47]

  2.1   Ligand engineering

  The photocatalytic efficiency of MOFs is intrinsically linked to the photoresponsive behavior of their organic ligands, which governs light absorption, charge generation, and carrier transport^[48]. Recent advances in MOF design have focused on π-conjugation extension, post-synthetic ligand modification, and charge-transfer pathway engineering to optimize their photophysical properties.

  To maximize solar energy utilization, extended π-conjugated architectures have been deliberately constructed in MOF ligands. A notable example is porphyrin-based Co-PMOFs, which integrate porphyrin and anthracene moieties to achieve panchromatic absorption (200-800 nm)^[17]. This design enables near-complete epoxide conversion (> 99%) within 6 h under ambient conditions while maintaining exceptional cyclic stability. The enhanced light-harvesting capability stems from the synergistic effect of dual π-conjugated systems, which promote efficient exciton generation and charge separation.

  Beyond the design of organic ligands themselves, precise modulation of the metal centers within macrocyclic ligand structures, such as porphyrins, represents a powerful sub-strategy under the umbrella of ligand engineering. Inspired by the molecular structure of chlorophyll, Das et al. integrated Mg²⁺ ions into the porphyrin ring to construct the PCN-224(Zr) catalyst. Under visible light irradiation, this material achieves 99% epoxide conversion, a 2.1-fold enhancement over the unmodified PCN-224 (47%) (Fig. 2a)^[49]. This case highlights how engineering the metal node of a ligand unit itself can dramatically tune the electronic structure and catalytic activity, showcasing an advanced facet of ligand engineering^[50].

  Figure 2

  

  Figure 2.  Catalyst structure diagram: (a) chlorophyll-inspired PCN-224 (Copyrighted from Ref. [49] with a license), (b) MOF-997 system (Copyrighted from Ref. [18] with a license), and (c) Fe-FcDC system (Copyrighted from Ref. [10] with a license)

  下载: 全尺寸图片 幻灯片

  Atomic-level control over MOFs′ catalytic sites can be achieved through post-synthetic ligand modification. A titanium-based MOF-901(Ti) was selectively oxidized at its imine bonds (C=N) to form amide linkages (—HN—CO—), yielding the novel MOF-997(Ti) (Fig. 2b)^[18]. The introduced amide groups establish donor-acceptor active sites with 1.8 eV higher CO₂ binding energy, resulting in a 99% cyclic carbonate yield, which is a 3.3-fold improvement over the parent MOF-901. While the fundamental light absorption onset might not shift dramatically, this electronic modification optimizes the utilization of photogenerated charges for the catalytic cycle, leading to a dramatic increase in yield. This approach demonstrates how subtle ligand alterations can fine-tune MOF electronic structures for superior photocatalytic performance.

  To mitigate charge recombination, redox-active ligands have been employed to construct multistage carrier transport channels. Zhang et al. developed Fe-FcDC, a ferrocene-based MOF featuring H₂FcDC ligands coordinated with FeO₆ clusters (Fig. 2c)^[10]. Unlike conventional organic linkers, FcDC introduces a metal-ligand-metal charge transfer pathway, which extends carrier migration distance and enhances photocurrent responsiveness. This design significantly improves photocatalytic CO₂ cycloaddition efficiency by facilitating long-range electron transfer and suppressing recombination losses.

  Thus, ligand engineering, through precise molecular design, stands as one of the most direct strategies to enhance the photocatalytic CO₂ cycloaddition performance of MOFs. By expanding the π-conjugated system, conducting post-synthetic modifications, and introducing redox-active units, it is possible to effectively broaden the light response range, promote charge separation and transfer, and optimize the adsorption and activation processes of reactants on active sites. However, the synthesis of complex ligands often involves cumbersome steps, low yields, and high costs, and highly conjugated or functionalized ligands may encounter photochemical stability issues under prolonged illumination.

  2.2   Composite construction

  Composite construction is the most effective and widely used way to solve the problems of insufficient active sites, poor charge separation, and limited mass transfer of MOFs to enhance the catalytic efficiency. Currently, three main strategies are employed: (1) interface engineering to optimize charge separation, (2) pore structure modulation to improve mass transfer efficiency, and (3) multicomponent synergy to enhance catalytic performance.

  In terms of interface design, molecular-level dispersion of Keggin-type phospho-molybdate (PMo₁₂) within the pores of zirconium ferrocene MOF (Zr-Fc) nanosheets forms the PMo₁₂@Zr-Fc composite (Fig. 3a)^[41]. This design enhances the electronic interaction between PMo₁₂ and the framework by utilizing the confinement effect of MOF pores, while retaining the high specific surface area and photoresponsiveness of Zr-Fc. It significantly increases the density of acid sites and optimizes cyclic stability through electrostatic binding, exhibiting a maximum cyclic carbonate yield of 298 mmol·g^-1·h^-1. Another typical example is the construction of W₁₈O₄₉/NH₂-UiO-66 type Ⅱ heterojunction using the in situ solvothermal method, where the interface charge directed transport and multi-active site synergy in photocatalytic reactions (Fig. 3b)^[30]. In the photocatalytic CO₂ cycloaddition reaction, the composite catalyst exhibited 82% conversion of styrene oxide with 58 mmol·g^-1·h^-1 yield of cyclic carbonate, which were 3.4 and 7.5 times greater than those of W₁₈O₄₉ and NH₂-UiO-66, respectively. NH₂-MIL-125(Ti) and FeNbO₄ constructed a heterojunction system with synergistic optimization of photon capture and carrier management through chemical modification and interface engineering, which achieves doubled cyclic carbonate yield compared to a single component^[31]. MIL-125@ZIF-67 S-scheme heterojunction catalysts, where the built-in electric field formed at the interface effectively suppresses the recombination of photogenerated carriers, achieving a final catalytic efficiency of 99% (Fig. 3c)^[32].

  Figure 3

  

  Figure 3.  Mechanism diagrams of photocatalytic cyclic carbonates production: (a) PMo₁₂@Zr-Fc (Copyrighted from Ref. [41] with a license), (b) W₁₈O₄₉/-NH₂UiO-66 (Copyrighted from Ref. [30] with a license), (c) MIL-125@ZIF-67 (Copyrighted from Ref. [32] with a license), (d) Co₂N_0.67@ZIF-67 (Copyrighted from Ref. [33] with a license), and (e) CMS@MOFs (Copyrighted from Ref. [35] with a license)

  下载: 全尺寸图片 幻灯片

  In response to the mass transfer limitations caused by the microporous structure of MOFs, Jiang et al. have developed a Co₂N_0.67@ZIF-67 composite by low-temperature pyrolysis of ZIF-67, where Co₂N_0.67 nanoparticles with photoconversion properties were generated in situ while maintaining the integrity of the main framework (Fig. 3d)^[33]. The material optimizes substrate mass transfer efficiency through open pores formed by partial ligand dissociation, resulting in a more than 4-fold yield increase in the cycloaddition reaction of epichlorohydrin compared to the original ZIF-67 (22%). Wang et al. developed a cobalt nanoparticle-encapsulated doped with N hierarchical mesoporous carbon/titanium dioxide/MXene composite through controlled pyrolysis of a multilayered ZIF/MXene precursor. The engineered mesoporous architecture enhanced mass diffusion and photogenerated carrier separation while inducing internal light reflection to boost photothermal conversion efficiency, achieving a 96% cyclic carbonate yield under full-spectrum irradiation^[34]. Substrate engineering provides an innovative solution to the problem of agglomeration in MOF photocatalysis. The CMS@MOFs composites exhibited enhanced mass transfer efficiency through a 3D interconnected pore network and hierarchical porosity design. The carbonized melamine sponge (CMS) substrate, with its high specific surface area, uniformly disperses MIL-88-NH₂/ZIF-8-NH₂ particles while preventing active site clogging. The hierarchical pore structure shortens reactant migration paths and reduces diffusion resistance (Fig. 3e)^[35].

  Therefore, constructing composite materials represents a powerful strategy to integrate the advantages of various components and achieve synergistic performance enhancement. It can simultaneously address multiple challenges faced by MOFs in photocatalysis, such as light harvesting, charge separation, and mass transfer. The current core challenge and future direction lie in the precise control of interfacial properties: how to rationally design and construct an ideal interface with strengthened chemical bonding and efficient carrier transport channels, rather than simple physical mixing.

  2.3   Dopant incorporation

  Dopant incorporation, involving the incorporation of metal or non-metal species into MOFs′ frameworks, has emerged as a powerful strategy to precisely tailor their electronic structure, light-harvesting properties, and catalytic activity.

  By incorporating highly charged ions^[51] or transition metals^[52], the band structure and charge carrier dynamics of MOFs can be effectively modulated. Zhai et al. designed a Bi³⁺-functionalized porphyrinic MOF PCN-224(Zr), boosting cyclic carbonate yield from 31% (pristine PCN-224(Zr)) to 99% within 6 h due to optimized CO₂ activation (Fig. 4a)^[43]. Rare-earth elements further introduce unique 4f-orbital electron configurations, enabling multi-electron transfer processes, as demonstrated by Tb³⁺-exchanged DBP(Co), which attains a 99.3% yield in CO₂ cycloaddition^[44]. Beyond metal doping, single-atom incorporation offers atomic-level precision in active site engineering. Atomic-level doping creates well-defined active sites without compromising framework integrity. Ⅴ-doped indium-based MOF SNNU-97(In) enhances CO₂ adsorption by 1.7 times and extends light absorption to 790 nm due to newly introduced electronic transitions (Fig. 4b)^[45]. Besides, non-metal doping (e.g., boron in zirconium-based MOF UiO-67-B)^[42] introduces distinct p-block electronic effects, enhancing Lewis acidity, charge separation, and chemisorption sites, leading to significantly accelerated reaction kinetics (Fig. 4c).

  Figure 4

  

  Figure 4.  Mechanism diagrams of photocatalytic cyclic carbonates production: (a) Bi-PCN-224 (Copyrighted from Ref. [43] with a license), (b) SNNU-97-InV (Copyrighted from Ref. [45] with a license), and (c) UiO-67-B (Copyrighted from Ref. [42] with a license)

  下载: 全尺寸图片 幻灯片

  Dopant incorporation could effectively adjust the electronic structure of MOFs, enabling fine control over their light absorption range, carrier concentration, and separation efficiency, as well as surface acidity, without altering the main framework structure. However, the challenge of this strategy lies in achieving uniform distribution of doping elements within the framework and precise control of doping concentration to avoid the formation of electron recombination centers or phase separation.

  3.   Future directions and challenges for MOF-based photocatalysts

  While significant progress has been achieved in developing MOF-based photocatalysts for CO₂-to-cyclic carbonate conversion, critical challenges remain that demand the establishment of a synergistic framework integrating photon harvesting, charge transport, and surface activation.

  For light absorption enhancement, breakthroughs beyond visible-light dependence require innovations at both molecular and mesoscopic levels. Bio-inspired designs mimicking chlorophyll′s broadband capture mechanisms could merge the bulk absorption advantages of narrow-bandgap semiconductors (e.g., black phosphorus, CuInS₂) with the localized field enhancement of plasmonic materials (e.g., Au nanorods, Ag nanocubes), constructing hierarchical photon-harvesting networks. Simultaneously, the confinement effects of MOFs′ pores may enable precise regulation of quantum dot size distribution and spatial orientation, optimizing exciton dissociation pathways for efficient near-infrared photon conversion.

  For the charge carrier′s management, cross-scale charge transport channels must be engineered: At the microscale, atomic layer deposition could tailor chemical bonding modes between MOFs and cocatalysts, designing low-barrier interfaces through orbital hybridization. At the mesoscale and macroscale, the foremost challenge currently is the precise modulation of interfacial dynamics between MOFs and other functional materials, such as semiconductors, carbon materials, and metal oxides, which critically influence photocatalytic performance. Existing methods for interfacial modulation lack the precision needed, leading to suboptimal charge transfer efficiency. Therefore, future endeavors should focus on developing advanced synthesis techniques like atomic layer deposition, exploring precise regulation methods such as molecular self-assembly, and refining interfacial structure design strategies. Furthermore, integrating in situ characterization with multiscale simulations will unravel the full dynamics of photogenerated carriers, from femtosecond-scale generation to millisecond-scale transport, establishing structure-activity models that correlate electronic states, interface density, and reaction pathways.

  Beyond material design, transitioning MOF-based photocatalysts from laboratory prototypes to industrial-scale applications presents multifaceted challenges. Key considerations include (1) the scalable and cost-effective synthesis of these often complex materials, (2) the long-term chemical and structural stability under continuous irradiation and in flow reactor systems, (3) engineering efficient photoreactors that ensure optimal light distribution and photon efficiency throughout the catalyst bed, and (4) conducting thorough techno-economic analysis and life-cycle assessment to validate the environmental and economic viability of the process compared to conventional thermal catalysis. Addressing these engineering and economic hurdles is equally as important as improving the catalyst′s intrinsic activity to realize the practical potential of MOFs-driven photocatalytic CO₂ valorization.

  These insights will inform the rational design of next-generation adaptive photocatalysts. Ultimately, converging material genomics with reactor engineering will catalyze the transition from laboratory prototypes to industrial-scale photoreactor systems, achieving sunlight-driven CO₂ valorization with atomic precision and macroscopic robustness.

  
  
• 1. [1]

     KHAN M, AKMAL Z, TAYYAB M, MANSOOR S, LIU D N, YE Z W, ZHANG J L, WU S Q, WANG L Z. Integration of CO₂ activation and photogenerated electron accumulation at Ti site via dual-tandem electric fields in BiOBr-MIL-125 heterojunction for boosting CO₂ photoreduction[J]. Appl. Catal. B-Environ., 2025, 370:  125165.

  2. [2]

     WANG D D, XU M Y, LIN Z X, WU J H, YANG W T, LI H J, SU Z M. One-pot synthesis of MIL-68(In)-derived CdIn₂S₄/In₂S₃ tubular heterojunction for highly selective CO₂ photoreduction[J]. Rare Metals, 2025, 44(6):  3956-3969.

  3. [3]

     LIU H, CHANG X L, YAN T, PAN W G. Research progress in catalytic conversion of CO₂ and epoxides based on ionic liquids to cyclic carbonates[J]. Nano Energy, 2025, 135:  110596.

  4. [4]

     HUANG K, ZHANG J Y, LIU F, DAI S. Synthesis of porous polymeric catalysts for the conversion of carbon dioxide[J]. ACS Catal., 2018, 8:  9079-9102.

  5. [5]

     ZHAO C C, SU X F, LI R H, YAN L K, SU Z M. Insight into the mechanism of CO₂ chemical fixation into epoxides by Windmill-shaped polyoxovanadate and n-Bu₄NX (X=Br, I)[J]. Inorg. Chem., 2024, 63(30):  14032-14039.

  6. [6]

     CAI M L, DAI S Y, XUAN J, MO Y M. Bromide-mediated membraneless electrosynthesis of ethylene carbonate from CO₂ and ethylene[J]. Nat. Commun., 2025, 16(1):  3285.

  7. [7]

     CHENG R L, WANG A H, SANG S X, LIANG H G, LIU S Q, TSIAKARAS P. Photocatalytic CO₂ cycloaddition over highly efficient W₁₈O₄₉-based composites: An economic and ecofriendly choice[J]. Chem. Eng. J., 2023, 466:  142982.

  8. [8]

     LI D D, KASSYMOVA M, CAI X C, ZANG S Q, JIANG H L. Photocatalytic CO₂ reduction over metal-organic framework-based materials[J]. Coordin. Chem. Rev., 2020, 412:  213262. doi: 10.1016/j.ccr.2020.213262

  9. [9]

     PRAJAPATI P K, KUMAR A, JAIN S L. First photocatalytic synthesis of cyclic carbonates from CO₂ and epoxides using CoPc/TiO₂ hybrid under mild conditions[J]. ACS Sustain. Chem. Eng, 2018, 6:  7799-7809. doi: 10.1021/acssuschemeng.8b00755

  10. [10]

      ZHANG H G, SI S H, ZHAI G Y, LI Y J, LIU Y Y, CHENG H F, WANG Z Y, WANG P, ZHENG Z K, DAI Y, LIU T X, HUANG B B. The long-distance charge transfer process in ferrocene-based MOFs with FeO₆ clusters boosts photocatalytic CO₂ chemical fixation[J]. Appl. Catal. B-Environ., 2023, 337:  122909.

  11. [11]

      YANG Q H, PENG H T, ZHANG Q J, QIAN X, CHEN X, TANG X, DAI S, ZHAO J J, JIANG K, YANG Q, SUN J, ZHANG L J, ZHANG N, GAO H L, LU Z Y, CHEN L. Atomically dispersed high-density Al-N₄ sites in porous carbon for efficient photodriven CO₂ cycloaddition[J]. Adv. Mater., 2021, 33(45):  2103186.

  12. [12]

      CHENG R L, NIU X Y, LI H, LIANG H G, TSIAKARAS P. Oxygen vacancy-rich defective tungsten oxide (WO_3-x) modified by Prussian blue for efficient photocatalytic carbon dioxide conversion and tetracycline degradation[J]. J. Colloid Interface Sci., 2025, 683:  807-816. doi: 10.1016/j.jcis.2024.12.146

  13. [13]

      LIN Y P, LI L, SHI Z, ZHANG L S, LI K, CHEN J M, WANG H, LEE J M. Catalysis with two-dimensional metal-organic frameworks: Synthesis, characterization, and modulation[J]. Small, 2024, 20(24):  2309841. doi: 10.1002/smll.202309841

  14. [14]

      ZHANG H, LI C, LANG F F, LI M, LIU H Y, ZHONG D C, QIN J S, DI Z Y, WANG D H, ZENG L, PANG J D, BU X H. Precisely tuning band gaps of hexabenzocoronene-based MOFs toward enhanced photocatalysis[J]. Angew. Chem.-Int. Edit., 2025, 64(6):  e202418017. doi: 10.1002/anie.202418017

  15. [15]

      SHEN Y, PAN T, WANG L, REN Z, ZHANG W N, HUO F W. Programmable logic in metal-organic frameworks for catalysis[J]. Adv. Mater., 2021, 33(46):  2007442. doi: 10.1002/adma.202007442

  16. [16]

      CUI W G, ZHANG G Y, HU T L, BU X H. Metal-organic framework-based heterogeneous catalysts for the conversion of C1 chemistry: CO, CO₂ and CH₄[J]. Coordin. Chem. Rev., 2019, 387:  79-120. doi: 10.1016/j.ccr.2019.02.001

  17. [17]

      LIANG J X, JIANG X, ZHANG X R, YU H, SHI J J, WANG M. Co-porphyrin-based metal-organic framework for light-driven efficient green conversion of CO₂ and epoxides[J]. Chem. Eng. J., 2024, 499:  156428. doi: 10.1016/j.cej.2024.156428

  18. [18]

      KEGERE J, ALNEYADI S S, PAZ A P, SIDDIG L A, ALBLOOSHI A, ALNAQBI M A, ALZAMLY A, GREISH Y E. Titanium metal-organic frameworks for photocatalytic CO₂ conversion through a cycloaddition reaction[J]. Nanoscale Adv., 2024, 6:  4804-4813. doi: 10.1039/D4NA00535J

  19. [19]

      HUANG Z W, HU K Q, MEI L, KONG X H, YU J P, LIU K, ZENG L W, CHAI Z F, SHI W Q. A mixed-ligand strategy regulates thorium-based MOFs[J]. Dalton Trans., 2020, 49(4):  983-987. doi: 10.1039/C9DT04158C

  20. [20]

      WU Y L, GAO L, ZHOU X C, YU X, MENG Y R, ZUO J L, SU J, YUAN S. Designing photothermal catalytic systems in multi-component MOFs for enhanced conversion of carbon dioxide[J]. Chem. Commun., 2024, 60(72):  9825-9828. doi: 10.1039/D4CC03203A

  21. [21]

      SHARMA N, DHANKHAR S S, NAGARAJA C M. A Mn(Ⅱ)-porphyrin based metal-organic framework (MOF) for visible-light-assisted cycloaddition of carbon dioxide with epoxides[J]. Microporous Mesoporous Mat., 2019, 280:  372-378. doi: 10.1016/j.micromeso.2019.02.026

  22. [22]

      SHI Q, CHEN M H, XIONG J, LI T, FENG Y Q, ZHANG B. Porphyrin-based two-dimensional metal-organic framework nanosheets for efficient photocatalytic CO₂ transformation[J]. Chem. Eng. J., 2024, 481:  148301. doi: 10.1016/j.cej.2023.148301

  23. [23]

      ZHANG H G, ZHAI G Y, LEI L F, ZHANG C Y, LIU Y Y, WANG Z Y, CHENG H F, ZHENG Z K, WANG P, DAI Y, HUANG B B. Photo-induced photo-thermal synergy effect leading to efficient CO₂ cycloaddition with epoxide over a Fe-based metal organic framework[J]. J. Colloid Interface Sci., 2022, 625:  33-41. doi: 10.1016/j.jcis.2022.05.146

  24. [24]

      ZHOU X L, ZHANG H G, CHENG H F, WANG Z Y, WANG P, ZHENG Z K, DAI Y, XING D N, LIU Y Y, HUANG B B. Enhanced cycloaddition between CO₂ and epoxide over a bismuth-based metal organic framework due to a synergistic photocatalytic and photothermal effect[J]. J. Colloid Interface Sci., 2024, 658:  805-814. doi: 10.1016/j.jcis.2023.12.112

  25. [25]

      LI L, LIU W X, SHI T, SHANG S, ZHANG X D, WANG H, TIAN Z Q, CHEN L, XIE Y. Photoexcited single-electron transfer for efficient green synthesis of cyclic carbonate from CO₂[J]. ACS Mater. Lett., 2023, 5(4):  1219-1226. doi: 10.1021/acsmaterialslett.3c00069

  26. [26]

      SIDDIG L A, ALZARD R H, NGUYEN H, GÖB C R, ALNAQBI M A, ALZAMLY A. Hexagonal layer manganese metal-organic framework for photocatalytic CO₂ cycloaddition reaction[J]. ACS Omega, 2022, 7(11):  9958-9963. doi: 10.1021/acsomega.2c00663

  27. [27]

      SIDDIG L A, ALZARD R H, ABDELHAMID A S, RAMACHANDRAN T, NGUYEN H, PAZ A P, ALZAMLY A. Cobalt hydrogen-bonded organic framework as a visible light-driven photocatalyst for CO₂ cycloaddition reaction[J]. Inorg. Chem., 2023, 62(38):  15550-15564. doi: 10.1021/acs.inorgchem.3c02051

  28. [28]

      LIU L F, ZHANG J L, CHENG X Y, XU M Z, KANG X C, WAN Q, HAN B X, WU N N, ZHENG L R, MA C Y. Amorphous NH₂-MIL-68 as an efficient electro- and photo-catalyst for CO₂ conversion reactions[J]. Nano Res., 2023, 16(1):  181-188. doi: 10.1007/s12274-022-4664-0

  29. [29]

      WU Z, GE Q M, CONG H, JIANG N, ZHAO W F, YANG S. Ligand-regulated oxygen vacancies in Ti-MOFs for visible-light-driven CO₂ cycloaddition to cyclic carbonates[J]. Sep. Purif. Technol., 2025, 366:  132831. doi: 10.1016/j.seppur.2025.132831

  30. [30]

      程若霖, 王浩然, 任静, 马莹莹, 梁华根. W₁₈O₄₉/NH₂-UiO-66复合催化剂的高效光催化CO₂环加成[J]. 无机化学学报, 2024,40,(3): 523-532. CHENG R L, WANG H R, REN J, MA Y Y, LIANG H G. Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst[J]. Chinese J. Inorg. Chem., 2024, 40(3):  523-532.

  31. [31]

      AHMED S H, BAKIRO M, ALZAMLY A. Photocatalytic activities of FeNbO₄/NH₂-MIL-125(Ti) composites toward the cycloaddition of CO₂ to propylene oxide[J]. Molecules, 2021, 26(6):  1693. doi: 10.3390/molecules26061693

  32. [32]

      SHEN Q Y, CHEN W R, WANG M, JIN X X, ZHANG L X, SHI J L. A MOF@MOF S-scheme heterojunction with Lewis acid-base sites synergistically boosts cocatalyst-free CO₂ cycloaddition[J]. ChemSusChem, 2025, 18(2):  .

  33. [33]

      JIANG L J, WU D Q, HUANG Z S, CHEN F F, CHEN K, IBRAGIMOV A B, GAO J K. In situ pyrolysis of ZIF-67 to construct Co₂N_0.67@ZIF-67 for photocatalytic CO₂ cycloaddition reaction[J]. Inorg. Chem., 2024, 63(31):  14761-14769. doi: 10.1021/acs.inorgchem.4c02504

  34. [34]

      WANG Y, DING M L, RONG W, KONG S Y, YAO J F. In situ growth of Fe-doped zeolitic imidazolate framework on MXene for boosting photodriven CO₂ cycloaddition[J]. Sep. Purif. Technol., 2024, 345:  127399. doi: 10.1016/j.seppur.2024.127399

  35. [35]

      DUAN C Y, XIE Y M, DING M L, FENG Y, YAO J F. Design of carbonized melamine sponge@MOFs composites bearing diverse acid-base properties for boosting thermal and solar-driven CO₂ cycloaddition[J]. J. CO₂ Util., 2022, 64:  102158. doi: 10.1016/j.jcou.2022.102158

  36. [36]

      GONG L, SUN J, LIU Y S, YANG G C. Photoinduced synergistic catalysis on Zn single-atom-loaded hierarchical porous carbon for highly efficient CO₂ cycloaddition conversion[J]. J. Mater. Chem. A, 2021, 9(38):  21689-21694. doi: 10.1039/D1TA06159C

  37. [37]

      WANG Y, DING M L, FU X T, YAO J F. High-efficiency photodriven coupling of CO₂ and various epoxides via a multi-shelled hollow ZIF/MXene derived composite with low activation energy[J]. Inorg. Chem. Front., 2025, 12(3):  1114-1124. doi: 10.1039/D4QI02269F

  38. [38]

      ZHU H Y, SHEN Q Y, YUAN Y Y, GAO H, ZHOU S, YANG F L, SUN L M, WANG X J, YI J J, HAN X G. Engineering the sulfide semiconductor/photoinactive-MOF heterostructure with a hollow cuboctahedral structure to enhance photocatalytic CO₂-epoxide-cycloaddition efficiency[J]. Inorg. Chem., 2024, 63(9):  4078-4085. doi: 10.1021/acs.inorgchem.3c03683

  39. [39]

      YANG G P, WU D, LU X M, TANG Y, GAO F, WANG Y Y. Light-assisted CO₂ cycloaddition over a nanochannel cadmium-organic framework loaded with silver nanoparticles[J]. ACS Appl. Nano Mater., 2023, 6(7):  6197-6207. doi: 10.1021/acsanm.3c00499

  40. [40]

      GUO Y C, FENG L, WU C C, WANG X M, ZHANG X. Confined pyrolysis transformation of ZIF-8 to hierarchically ordered porous Zn-N-C nanoreactor for efficient CO₂ photoconversion under mild conditions[J]. J. Catal., 2020, 390:  213-223. doi: 10.1016/j.jcat.2020.07.037

  41. [41]

      FANG Z, DENG Z, WAN X Y, LI Z Y, MA X, HUSSAIN S, YE Z Z, PENG X S. Keggin-type polyoxometalates molecularly loaded in Zr-ferrocene metal organic framework nanosheets for solar-driven CO₂ cycloaddition[J]. Appl. Catal. B-Environ., 2021, 296:  120329. doi: 10.1016/j.apcatb.2021.120329

  42. [42]

      LI Y J, ZHAI G Y, LIU Y Y, WANG Z Y, WANG P, ZHENG Z K, CHENG H F, DAI Y, HUANG B B. Synergistic effect between boron containing metal-organic frameworks and light leading to enhanced CO₂ cycloaddition with epoxides[J]. Chem. Eng. J., 2022, 437(1):  135363.

  43. [43]

      ZHAI G Y, LIU Y Y, LEI L F, WANG J J, WANG Z Y, ZHENG Z K, WANG P, CHENG H F, DAI Y, HUANG B B. Light-promoted CO₂ conversion from epoxides to cyclic carbonates at ambient conditions over a bi-based metal-organic framework[J]. ACS Catal., 2021, 11(4):  1988-1994. doi: 10.1021/acscatal.0c05145

  44. [44]

      SHI Q, XU Y H, CHEN M H, ZHAO P, DENG W B, XIONG J, GUO K, FENG Y Q, ZHANG B. A versatile synthetic strategy towards rare earth based metal-organic frameworks[J]. Sci. China Chem., 2025, 68(4):  1362-1371. doi: 10.1007/s11426-024-2322-9

  45. [45]

      FAN S C, CHEN S Q, WANG J W, LI Y P, ZHANG P, WANG Y, YUAN W Y, ZHAI Q G. Precise introduction of single vanadium site into indium-organic framework for CO₂ capture and photocatalytic fixation[J]. Inorg. Chem., 2022, 61:  14131-14139. doi: 10.1021/acs.inorgchem.2c02250

  46. [46]

      ZHAI G Y, LIU Y Y, MAO Y Y, ZHANG H G, LIN L T, LI Y J, WANG Z Y, CHENG H F, WANG P, ZHENG Z K, DAI Y, HUANG B B. Improved photocatalytic CO₂ and epoxides cycloaddition via the synergistic effect of Lewis acidity and charge separation over Zn modified UiO-bpydc[J]. Appl. Catal. B-Environ., 2022, 301:  120793. doi: 10.1016/j.apcatb.2021.120793

  47. [47]

      HUANG Z W, HU K Q, MEI L, WANG C Z, CHEN Y M, WU W S, CHAI Z F, SHI W Q. Potassium ions induced framework interpenetration for enhancing the stability of uranium-based porphyrin MOF with visible-light-driven photocatalytic activity[J]. Inorg. Chem., 2021, 60(2):  652-660.

  48. [48]

      FANG Z B, LIU T T, LIU J X, JIN S Y, WU X P, GONG X Q, WANG K C, YIN Q, LIU T F, CAO R, ZHOU H C. Boosting interfacial charge-transfer kinetics for efficient overall CO₂ photoreduction via rational design of coordination spheres on metal-organic frameworks[J]. J. Am. Chem. Soc., 2020, 142(28):  12515-12523. doi: 10.1021/jacs.0c05530

  49. [49]

      DAS R, MANNA S S, PATHAK B, NAGARAJA C M. Strategic design of Mg-centered porphyrin metal-organic framework for efficient visible light-promoted fixation of CO₂ under ambient conditions: Combined experimental and theoretical investigation[J]. ACS Appl. Mater. Interfaces, 2022, 14(29):  33285-33296. doi: 10.1021/acsami.2c07969

  50. [50]

      CUI W G, HU T L. Incorporation of active metal species in crystalline porous materials for highly efficient synergetic catalysis[J]. Small, 2021, 17:  2003971. doi: 10.1002/smll.202003971

  51. [51]

      LIU C, CHEN H L, CHEN Q, BI J H, YU J C, WU L. Active site modulation in UiO-66(Ce) MOFs by Al³⁺ doping for boosting photocatalysis[J]. J. Catal., 2024, 437:  115670. doi: 10.1016/j.jcat.2024.115670

  52. [52]

      ZHANG Y Y, HUANG R T, FANG Y, WANG J C, YUAN Z J, CHEN X W, ZHU W J, CAI Y, SHI X Y. Modulation of Fe-MOF via second-transition metal ion doping (Ti, Mn, Zn, Cu) for efficient visible-light driven CO₂ reduction to CH₄[J]. Sep. Purif. Technol., 2024, 336:  126164. doi: 10.1016/j.seppur.2023.126164

• 

  Figure 1  Two mechanism diagrams of the photocatalytic CO₂ cycloaddition reaction: (a) radical-anion pathway and (b) epoxide-activation pathway

  下载: 全尺寸图片 幻灯片
  

  Figure 2  Catalyst structure diagram: (a) chlorophyll-inspired PCN-224 (Copyrighted from Ref. [49] with a license), (b) MOF-997 system (Copyrighted from Ref. [18] with a license), and (c) Fe-FcDC system (Copyrighted from Ref. [10] with a license)

  下载: 全尺寸图片 幻灯片
  

  Figure 3  Mechanism diagrams of photocatalytic cyclic carbonates production: (a) PMo₁₂@Zr-Fc (Copyrighted from Ref. [41] with a license), (b) W₁₈O₄₉/-NH₂UiO-66 (Copyrighted from Ref. [30] with a license), (c) MIL-125@ZIF-67 (Copyrighted from Ref. [32] with a license), (d) Co₂N_0.67@ZIF-67 (Copyrighted from Ref. [33] with a license), and (e) CMS@MOFs (Copyrighted from Ref. [35] with a license)

  下载: 全尺寸图片 幻灯片
  

  Figure 4  Mechanism diagrams of photocatalytic cyclic carbonates production: (a) Bi-PCN-224 (Copyrighted from Ref. [43] with a license), (b) SNNU-97-InV (Copyrighted from Ref. [45] with a license), and (c) UiO-67-B (Copyrighted from Ref. [42] with a license)

  下载: 全尺寸图片 幻灯片

  Table 1.  Performance comparison of MOFs for photocatalytic CO₂ cycloaddition

  Catalyst	Light source	Time /h	Reaction substrate	Conversion /%	Yield /(mmol·g-1·h-1)	Regulatory strategy	Ref.
  Fe-FcDC	300 W xenon lamp	4	Epichlorohydrin	7	44	Ligand engineering	[10]
  Co-PMOF 3	300 W xenon lamp	6	Epichlorohydrin	> 99	61	Ligand engineering	[17]
  MOF-997	300 W xenon lamp	24	Styrene oxide	> 99	2	Ligand engineering	[18]
  Th-IHEP-5	45 W fluorescent light	48	Styrene oxide	71	0.6	Ligand engineering	[19]
  Zr-TTF-L1	300 W xenon lamp	8	Propylene oxide	45	14	Ligand engineering	[20]
  MOF 1 (Mn)	LED 18×3W	24	Epichlorohydrin	100	17	Ligand engineering	[21]
  Fe-DBP(Co)	1000 W xenon lamp	12	Epichlorohydrin	97	103	Ligand engineering	[22]
  FeTPyP	300 W xenon lamp	5	Styrene oxide	30	106	Ligand engineering	[23]
  Bi-HHTP	300 W xenon lamp	4	Styrene oxide	34	112	Ligand engineering	[24]
  Mg-MOF-74	400 mW·cm-2	12	1-Bromo-2,3-epoxypropane	97	5	Ligand engineering	[25]
  UAEU-50	400 W halogen lamp	24	Styrene oxide	90	6	Ligand engineering	[26]
  Co-HOF	400 W halogen lamp	24	Styrene oxide	> 99	6	Ligand engineering	[27]
  NH2-MIL-68	300 W xenon lamp	12	Styrene oxide	94	56	Ligand engineering	[28]
  Ti-H2TPDC	8 W LED light	4	Epichlorohydrin	94	59	Ligand engineering	[29]
  PB-modified WO3-x	300 W xenon lamp	8	Styrene oxide	94	171	Composite construction	[12]
  W18O49/NH2-UiO-66	300 W xenon lamp	4	Styrene oxide	82	58	Composite construction	[30]
  FeNbO4/NH2-MIL-125(Ti)	500 W halogen lamp	72	Propylene oxide	52	0.2	Composite construction	[31]
  MIL-125@ZIF-67	3 W blue LED	36	1-Bromo-2,3-epoxypropane	99	0.3	Composite construction	[32]
  Co2N0.67@ZIF-67	350 mW·cm-2	3	Epichlorohydrin	95	3	Composite construction	[33]
  Zn20Fe1-ZIF/MXene	350 mW·cm-2	6	Epichlorohydrin	96	16	Composite construction	[34]
  CMS@MIL-88-NH2	300 W xenon lamp	6	1, 2-Epoxybutane	72	24	Composite construction	[35]
  Zn SA-NC	300 mW·cm-2	16	Epichlorohydrin	99	0.5	Composite construction	[36]
  CoNHPC/TM-8	350 mW·cm-2	12	Styrene oxide	99	8	Composite construction	[37]
  CuS@HKUST-1	Blue light	18	2-Chloromethyl-oxriane	98	11	Composite construction	[38]
  Ag0.1/NWU-Cd3a	300 W xenon lamp	6	Styrene oxide	94	22	Composite construction	[39]
  Zn-N-HOPCPs	350 mW·cm-2	10	Propylene oxide	95	29	Composite construction	[40]
  PMo12@Zr-Fc	500 mW·cm-2	8	Epichlorohydrin	96	298	Composite construction	[41]
  UiO-67-B	300 W xenon lamp	6	Propylene epoxide	6	45	Dopant incorporation	[42]
  Bi-PCN-224	300 W xenon lamp	6	Propylene epoxide	99	5	Dopant incorporation	[43]
  Tb-DBP(Co)	300 W xenon lamp	10	Epichlorohydrin	> 99	127	Dopant incorporation	[44]
  SNNU-97-InV	300 W xenon lamp	24	2-Bromooxirane	97	14	Dopant incorporation	[45]
  Zn-UiO-bpydc	300 W xenon lamp	9	Propylene oxide	75	0.3	Dopant incorporation	[46]
  IHEP-9	45 W compact fluorescent lamp	12	Styrene oxide	99	2	Dopant incorporation	[47]

  下载: 导出CSV
•