Metal-organic Frameworks Photocatalysts Research Articles

Enhanced C(sp3)–H Selective Oxidation Using Efficient Polyoxometalate-Based Metal–Organic Framework Photocatalysts Synergized with Ir Metalloligands and Polyoxometalates

Enhanced C(sp³)–H Selective Oxidation Using Efficient Polyoxometalate-Based Metal–Organic Framework Photocatalysts Synergized with Ir Metalloligands and Polyoxometalates

Designing 1-nm-Thick MOF Nanosheets with Donor-Acceptor Complexes for Photosynthesis of H2O2 Using Water and Dioxygen Only.

Artificial photosynthesis of hydrogen peroxide (H2O2) presents a promising environmentally friendly alternative to the industrial anthraquinone process. This work designed ultrathin metal-organic framework (MOF) nanosheets on which porphyrin ligand as an electron donor (D) and anthraquinone (AQ) as an electron acceptor (A) are integrated as the D-A complexes. The porphyrin component allows the MOF nanosheets to absorb full-spectrum solar light while the acceptor AQ motif promotes central aluminum ion coordination, hindering layer stacking to achieve a thickness of 1.0 nm. The ultrathin D-A design facilitates the separation of electrons from the MOF skeleton to the AQ motif, which induces the direct two-electron oxygen reduction reaction (ORR) mediated by the reversible redox couple of AQ-AQH2 and multielectron water oxidation reaction (WOR) driven by holes remaining on the porphyrin part. In O2-saturated water, the ultrathin MOF nanosheets outperformed the AQ-free bulk and multilayered counterparts by 2.9 and 2.6 times in H2O2 production, respectively, achieving the apparent quantum yield of 4.8% at 420 nm. It also surpasses other benchmark photocatalysts, including the typical MOF photocatalyst, MIL-125-NH2, and organic polymeric photocatalysts. The ultrathin D-A MOF photocatalyst generated H2O2 via both two-electron ORR as a major path and two-electron WOR as a minor path. This approach presents a promising strategy for the rational design of efficient nanostructured photocatalysts for solar fuels and chemicals.

Peptide-Guided Metal-Organic Frameworks Spatial Assembly Sustain Long-Lived Charge-Separated State to Improve Photocatalytic Performance.

The controlled fabrication of spatial architectures using metal-organic framework (MOF)-based particles offers opportunities for enhancing photocatalytic performances. The understanding of the contribution of assembly to a precise photocatalytic mechanism, particularly from the perspective of charge separation and extraction dynamics, still poses challenges. The present report presents a facile approach for the spatial assembly of zinc imidazolate MOF (ZIF-8), guided by β-turn peptides (SAZH). We investigated the dynamics of photoinduced carriers using transient absorption spectroscopy. The presence of a long-lived internal charge-separated state in SAZH confirms its role as an intersystem crossing state. The formation of an assembly interface facilitates efficient electron transfer from SAZH to O2, resulting in approximately 2.6 and 2 times higher concentrations of superoxide (·O2-) and hydrogen peroxide (H2O2), respectively, compared to those achieved with ZIF-8. The medical dressing fabricated from SAZH demonstrated exceptional biocompatibility and exhibited an outstanding performance in promoting wound restoration. It rapidly achieved hemostasis during the bleeding phase, followed by a nearly 100% photocatalytic killing efficiency against the infected site during the subsequent inflammatory phase. Our findings reveal a pivotal dynamic mechanism underlying the photocatalytic activity of control-assembled ZIF-8, providing valuable guidelines for the design of highly efficient MOF photocatalysts.

Customization of indium-based MOFs for enhanced adsorptive and photocatalytic of organic pollutants: Morphology involvement on performance and mechanism

Metal-organic frameworks (MOFs) as photocatalysts are promising candidates for environmental wastewater treatment owing to their tunable crystal structure, well-ordered donor–acceptor interface, and exceptional porosity. However, precise control over size and morphologies of MOFs to enhance adsorptive and photocatalytic performance is still a considerable challenge. Herein, the MIL-68(In)–NH2 (MN) MOFs with special acicular structure are customized by a facile method, in which the growth of crystal nuclei is inhibited and regulated by pyridine. The formation mechanism of MN with different morphologies and size is introduced, and their photocatalytic activities are systematically explored by degrading model pollutants tetracycline (TC) and dyes under visible light irradiation. Benefiting from its high specific surface area and the exposed large lattice spacing facet, the wool-ball morphology MN (MN-W) with surface acicular nanostructure presents an optimum photocatalytic performance compared to other MN morphologies. The MN-W also exhibits excellent adsorption capacity, remarkable cyclic stability, and good practical organic wastewater treatment capability. The possible photodegradation mechanism and pathways are elucidated, demonstrating that h+ is the primary reactive species, followed by •OH and •O2– radicals, responsible for the degradation of TC. This work is anticipated to tailoring design and modulate MOF photocatalysts for boosting the photocatalytic performance towards organic effluents remediation.

Molecular Engineering of Metal-Organic Frameworks for Boosting Photocatalytic Hydrogen Peroxide Production.

The development of novel metal-organic frameworks (MOFs) as efficient photocatalysts for hydrogen peroxide production from water and oxygen is particularly interesting, yet remains a challenge. Herein, we have prepared four cyclic trinuclear units (CTUs) based MOFs, exhibiting good light absorption ability and suitable band gaps for photosynthesis of H2O2. However, Cu-CTU-based MOFs are not able to photocatalyzed the formation of H2O2, while the alteration of metal nodes from Cu-CTU to Ag-CTU dramatically enhances the photocatalytic performance for H2O2 production and the production rates can reach as high as 17476 μmol g-1 h-1 with an apparent quantum yield of 4.72 %, at 420 nm, which is much higher than most reported MOFs. The photocatalytic mechanism is comprehensively studied by combining the isotope labeling experiments and DFT calculation. This study provides new insights into the preparation of MOF photocatalysts with high activity for H2O2 production through molecular engineering.

Molecular Engineering of Metal–Organic Frameworks for Boosting Photocatalytic Hydrogen Peroxide Production

AbstractThe development of novel metal–organic frameworks (MOFs) as efficient photocatalysts for hydrogen peroxide production from water and oxygen is particularly interesting, yet remains a challenge. Herein, we have prepared four cyclic trinuclear units (CTUs) based MOFs, exhibiting good light absorption ability and suitable band gaps for photosynthesis of H2O2. However, Cu‐CTU‐based MOFs are not able to photocatalyzed the formation of H2O2, while the alteration of metal nodes from Cu‐CTU to Ag‐CTU dramatically enhances the photocatalytic performance for H2O2 production and the production rates can reach as high as 17476 μmol g−1 h−1 with an apparent quantum yield of 4.72 %, at 420 nm, which is much higher than most reported MOFs. The photocatalytic mechanism is comprehensively studied by combining the isotope labeling experiments and DFT calculation. This study provides new insights into the preparation of MOF photocatalysts with high activity for H2O2 production through molecular engineering.

Incorporation anthracene and Cu to NH2-Zr-UiO-67 metal-organic framework: Introducing the simultaneous selectivity and efficiency in photocatalytic CO2 reduction to ethanol

Metal-organic frameworks (MOFs) are considered promising candidates for photocatalytic CO2 reduction (PCR) into valuable organic fuels. However, compared to numerous reports regarding CO, CH4, and CHOOH generation, the explored MOFs have shown limited success in producing alcohols, particularly EtOH, through the PCR strategy. Existing MOFs also suffer from insufficient selectivity and efficiency. This study addresses these limitations by implementing a dual modification strategy on NH2-Zr-UiO-67 MOFs. This strategy involves synthesizing four MOF derivatives with different ratios of redox-active metal sites (Cu) to light absorption antenna (anthracene): 1:1, 2:1, 1:2, and 1:3. The as-synthesized MOFs (denoted as Cu/An (X:X)@NZU67 exhibited a remarkable capability for PCR-to-EtOH, without requiring a photosensitizer. The optimal amount of anthracene plays a crucial role in several aspects: improving light absorption, enhancing CO2 adsorption capacity, and promoting charge transfer/separation. Efficient charge transfer is critical for facilitating the multi-step electron transfer pathway required for ethanol synthesis. Notably, Cu/An (1:2)@NZU67 achieved an ethanol productivity of 624.17 µmolh−1g−1 for EtOH, which is, to the best of our knowledge, the highest efficiency reported for MOFs in PCR-to-EtOH conversion so far. Besides significant performance, the MOF showed 100% selectivity for EtOH production. This work represents a significant milestone in the field of PCR-to-EtOH transformation by providing a new perspective for designing MOF photocatalysts that can simultaneously improve both selectivity and efficiency.

Crystal-Defect-Induced Longer Lifetime of Excited States in a Metal-Organic Framework Photocatalyst to Enhance Visible-Light-Mediated CO2 Reduction.

We report the structural defects in Zr-metal-organic framework (MOFs) for achieving highly efficient CO2 reduction under visible light irradiation. A series of defective Zr-MOF-X (X = 160, 240, 320, or 400) are synthesized by acid-regulated defect engineering. Compared to pristine defect-free Zr-MOF (NNU-28), N2 uptake increases for Zr-MOF-X synthesized with the HAc modulator, producing a larger pore space and Brunauer-Emmett-Teller surface area. The pore size distribution demonstrates that defective Zr-MOF-X exhibits mesoporous structures. Electrochemistry tests show that defective Zr-MOF-X possesses a more negative reduction potential and a higher photocurrent responsive signal than that of pristine NNU-28. Consequently, the defective samples exhibit a significantly higher efficiency in the photoreduction of CO2 to formate. Transient absorption spectroscopies manifest that structural defects modulate the excited-state behivior of Zr-MOF-X and improve the photogenerated charge separation of Zr-MOF-X. Furthermore, electron paramagnetic resonance and in-suit X-ray photoelectron spectroscopy provide additional evidence of the high photocatalytic performance exhibited by defective Zr-MOF-X. Results demonstrate that structural defects in Zr-MOF-X also improve the charge transfer, producing abundant Zr(III) catalytically active sites, exhibiting a slower decay process than defect-free Zr-MOF. The long-lifetime Zr(III) species in defective Zr-MOF-X are fully exposed to a high-concentration CO2 atmosphere, thereby enhancing the photocatalytic efficiency of CO2 reduction.

Synthesis of NH2-UiO-66/Bi4O5I2 heterojunction for high tetracycline reduction under visible light

In this study, direct Z-scheme NH2-UiO-66/Bi4O5I2 heterostructures were successfully synthesized to harness visible light for the degradation of tetracycline (TC), thereby evaluating the photocatalytic activity of the materials. NH2-UiO-66/Bi4O5I2 demonstrated robust photocatalytic efficacy under visible light irradiation, with NU/BOI-80 exhibiting the highest TC removal rate (91 %) within 120 min. Through UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS) and Photoluminescence (PL) diagram analysis, it was found that NH2-UiO-66/Bi4O5I2 shows good photocatalytic properties. Mott-Schottky and electrochemical impedance spectroscopy (EIS) indicated the enhanced separation efficiency of electron-hole pairs within the material, thereby mitigating recombination losses. In addition, free radical capture experiments and the combination of electron spin resonance (ESR) showed that ·O2−and h+ were the main active species. At the same time, NH2-UiO-66/Bi4O5I2 has been confirmed to have good stability. Finally, a proposed photocatalytic electron transfer mechanism was formulated based on the characterization and experimental results. This study presents a promising avenue for leveraging metal-organic framework photocatalysts for the effective removal of TC.

Preparation of a Nanosheeted Uranyl-Organic Framework for Enhanced Photocatalytic Oxidation of Toluene.

Preparation of ultrathin metal-organic framework (MOF) nanosheets is an effective way to improve the catalytic efficiency of MOF photocatalysts owing to their superiority in reducing the recombination rate of photogenerated electrons and holes and enhancing charge transfer. Herein, a light-sensitive two-dimensional uranyl-organic framework named HNU-68 was synthesized. Due to its interlayer stacking structure, the corresponding ultrathin nanosheets with a thickness of 4.4 nm (HNU-68-N) can be obtained through ultrasonic exfoliation. HNU-68-N exhibited an enhanced ability to selectively oxidize toluene to benzaldehyde, with the value of turnover frequency being approximately three times higher than that of the bulk HNU-68. This enhancement is attributed to the smaller size and interface resistance of the layered HNU-68-N nanosheets, which facilitate more thorough substrate contact and faster charge transfer, leading to an improvement in the photocatalytic efficiency. This work provides a potential candidate for the application of ultrathin uranyl-based nanosheets.

Single-Atom based Metal-Organic Framework Photocatalysts for Solar-Fuel Generation.

The growing demand for fossil fuels and subsequent CO2 emissions prompted a search for alternate sources of energy and a reduction in CO2. Photocatalysis driven by solar light has been found as a potential research area to tackle both these problems. In this direction, SAC@MOF (Single-atom loaded MOFs) photocatalysis is an emerging field and a promising technology. The unique properties of single-atom catalysts (SACs), such as high catalytic activity and selectivity, are leveraged in these systems. Photocatalysis, focusing on the utilization of Metal-Organic Frameworks (MOFs) as platforms for creating single-atom catalysts (SACs) characterized by metal single-atoms (SAs) as their active sites, are noted for their unparalleled atomic efficiency, precisely defined active sites, and superior photocatalytic performance. The synergy between MOFs and SAs in photocatalytic systems is meticulously examined, highlighting how they collectively enhance photocatalytic efficiency. This review examines SAC@MOF development and applications in environmental and energy sectors, focusing on synthesis and stabilization methods for SACs on MOFs and also characterization techniques vital for understanding these catalysts. The potential of SAC@MOF in CO2 Photoreduction and Photocatalytic H2 evolution is highlighted, emphasizing its role in green energy technologies and advances in materials science and Photocatalysis.

Water-Stable High-Entropy Metal-Organic Framework Nanosheets for Photocatalytic Hydrogen Production.

Metal-organic frameworks (MOFs) have emerged as promising platforms for photocatalytic hydrogen evolution reaction (HER) due to their fascinating physiochemical properties. Rationally engineering the compositions and structures of MOFs can provide abundant opportunities for their optimization. In recent years, high-entropy materials (HEMs) have demonstrated great potential in the energy and environment fields. However, there is still no report on the development of high-entropy MOFs (HE-MOFs) for photocatalytic HER in aqueous solution. Herein, the authors report the synthesis of a novel p-type HE-MOFssingle crystal (HE-MOF-SC) and the corresponding HE-MOFsnanosheets (HE-MOF-NS) capable of realizing visible-light-driven photocatalytic HER. Both HE-MOF-SC and HE-MOF-NS exhibit higher photocatalytic HER activity than all the single-metal MOFs, which are supposed to be ascribed to the interplay between the different metal nodes in the HE-MOFsthat enables more efficient charge transfer. Moreover, impressively, the HE-MOF-NS demonstrates much higher photocatalytic activity than the HE-MOF-SC due to its thin thickness and enhanced surface area. At optimum conditions, the rate of H2 evolution on the HE-MOF-NS is ≈13.24 mmol h-1 g-1, which is among the highest values reported for water-stable MOF photocatalysts. This work highlights the importance of developing advanced high-entropy materials toward enhanced photocatalysis.

Manipulating the Spin State of Co Sites in Metal-Organic Frameworks for Boosting CO2 Photoreduction.

Photocatalytic CO2 reduction holds great potential for alleviating global energy and environmental issues, where the electronic structure of the catalytic center plays a crucial role. However, the spin state, a key descriptor of electronic properties, is largely overlooked. Herein, we present a simple strategy to regulate the spin states of catalytic Co centers by changing their coordination environment by exchanging the Co species into a stable Zn-based metal-organic framework (MOF) to afford Co-OAc, Co-Br, and Co-CN for CO2 photoreduction. Experimental and DFT calculation results suggest that the distinct spin states of the Co sites give rise to different charge separation abilities and energy barriers for CO2 adsorption/activation in photocatalysis. Consequently, the optimized Co-OAc with the highest spin-state Co sites presents an excellent photocatalytic CO2 activity of 2325.7 μmol·g-1·h-1 and selectivity of 99.1% to CO, which are among the best in all reported MOF photocatalysts, in the absence of a noble metal and additional photosensitizer. This work underlines the potential of MOFs as an ideal platform for spin-state manipulation toward improved photocatalysis.

Application of graphdiyne for promote efficient photocatalytic hydrogen evolution

The photocatalytic hydrogen evolution technology converts solar energy into clean and environmentally friendly hydrogen energy, which is considered an effective means to solve environmental pollution and energy crisis. The unique sp and sp2 hybrid carbon network structure of graphdiyne endows it with excellent carrier mobility, and high porosity, making it a promising photocatalytic material for solar energy conversion. This article provides a detailed description of the unique structural properties and adjustable bandgap of graphdiyne. In addition, a detailed review was provided on the modification strategies of graphdiyne based catalysts for photocatalytic hydrogen evolution, including titanium based photocatalysts, metal oxide photocatalysts, double hydroxide catalysts, metal organic framework photocatalysts and other typical semiconductors. Finally, the challenges and opportunities for developing graphdiyne semiconductors for photocatalytic water splitting were proposed. Timely review is expected to contribute to the rapid development of graphdiyne in the field of photocatalytic hydrogen evolution.

Porphyrin-Based Two-Dimensional Metal-Organic framework nanosheets for efficient photocatalytic CO2 transformation

2D metal − organic framework (MOF) nanosheets have been demonstrated to exhibit excellent properties and prospects in various aspects, especially in photocatalysis. However, the design and direct preparation of 2D MOF photocatalyst is highly desirable but still challenging. Herein, a novel 2D porphyrin-based MOF Fe-DBP(Co), which is assembled by dicarboxylic porphyrin ligands and the unprecedented undecametallic ferric-oxo clusters, is designed and developed. The unique nanosheet morphology and assembled layered structure endows the photocatalyst with higher electron-hole separation efficiency and longer photogenerated carrier lifetime compared to the analogous MOFs. Consequently, Fe-DBP(Co) exhibits strikingly excellent and stable photocatalytic performance in CO2 cycloaddition, and the reaction rate of 103.2 mmol∙g−1∙h−1 is among the state-of-the-art cases for MOF-photocatalyzed CO2 cycloaddition. The underlying mechanism investigation suggested that photogenerated electrons transferred from CoDBP ligands to the Fe clusters, and the abundant electrons and holes promoted the generation of Fe(II) and Co(III) respectively, leading to excellent catalytic performance. This work proposes a new strategy to design and develop efficient MOF photocatalysts for photocatalytic transformation of CO2.

Integrative analysis of multi machine learning models for tetracycline photocatalytic degradation with MOFs in wastewater treatment

This study focuses on the utilization of connectionist models, specifically Independent Component Analysis (ICA), Genetic Algorithm (GA), Particle Swarm Optimization (PSO), and Genetic Algorithm-Particle Swarm Optimization (GAPSO) integrated with a least-squares support vector machine (LSSVM) to forecast the degradation of tetracycline (TC) through photocatalysis using Metal-Organic Frameworks (MOFs). The primary objective of this study was to evaluate the viability and precision of these connectionist models in estimating the efficiency of TC degradation, particularly within the context of wastewater treatment. The input parameters for these models cover essential MOF characteristics, such as pore size and surface area, along with critical operational factors, such as pH, TC concentration, catalyst dosage, and illumination duration, all of which are linked to the photocatalytic performance of MOFs. Sensitivity analysis revealed that the illumination duration is the primary influencer of TC photodegradation with MOF photocatalysts, while the MOFs’ surface area is the second crucial parameter shaping the efficiency and dynamics of the TC-MOF photocatalytic system. The developed LSSVM models display impressive predictive capabilities, effectively forecasting the experimental degradation of TC with high accuracy. Among these models, the GAPSO-LSSVM model excels as the top performer, achieving notable evaluation metrics, including STD, RMSE, MSE, MRE, and R2 at values of 3.09, 3.42, 11.71, 5.95, and 0.986, respectively. In comparison, the PSO-LSSVM, ICA-LSSVM, and GA-LSSVM models yield mean relative errors of 6.18%, 7.57%, and 11.37%, respectively. These outcomes highlight the exceptional predictive capabilities of the GAPSO-LSSVM model, solidifying its position as the most accurate and dependable model for predicting TC photodegradation in this study. This study contributes to advancing photocatalytic research and effectively reinforces the importance of leveraging machine learning methodologies for tackling environmental challenges.

Enhanced Intermolecular Electron Transfer in Fluorinated Metal–Organic Framework Photocatalysts for Efficient CO2 Reduction

AbstractEfficient electron transfer from photosensitizer to catalytic sites is crucial for effective artificial photosynthesis, yet it remains a significant challenge. Herein, it is reported that simple fluorination of the organic linkers in the MIL‐101(Fe) photocatalyst results in a remarkable threefold increase in the photocatalytic CO2‐to‐CO conversion rate (688 µmol g−1 h−1) compared to the pristine counterpart (230 µmol g−1 h−1). It is unveiled that, instead of directly modifying the electron structure of MIL‐101(Fe), the fluorinated linkers enhance the interaction between the discrete photocatalyst and photosensitizer ([Ru(bpy)3]2+, bpy = 2,2'‐bipyridine) via hydrogen bonding, thereby facilitating their intermolecular electron transfer. Most importantly, it is also demonstrated that this performance boosting strategy can be applied to other Fe‐based metal–organic frameworks (MOFs) photocatalysts such as MIL‐53(Fe) and MIL‐88(Fe). The present work not only underscores the fluorination of organic linkers as a generic promising approach to enhance the photocatalytic performance of MOF‐based catalysts, but also holds significant implications for photosynthesis and catalytic processes reliant on intermolecular electron transfer as an important step.

Novel layer-to-layer charge transfer in an anion-pillared metal-organic framework for efficient CO2 photoreduction to CH4

The highly selective photoreduction of CO2 to CH4 is hindered by the sluggish eight-electron transfer process and rapid recombination of charge carriers. Herein, an anion-pillared metal–organic framework photocatalyst, CuSiF6-TPPY, is judiciously constructed for the highly selective photoreduction of CO2 to CH4. The polar SiF62− pillars significantly enhance the CO2 adsorption capacity to 96.56 cm3 g−1. Furthermore, the incorporation of SiF62− pillars separates the HOMO and LUMO energy levels in distinct MOF layers, leading to a lower energy barrier for *CHO generation and a higher energy barrier for CO desorption. As a result, CuSiF6-TPPY delivers a CH4 generation rate of 13.84 μmol g−1 h−1 with a high selectivity of 88.78 %, 4-times higher than TPPY ligands. Moreover, in-situ IR spectra and computational simulations further confirm the photoreduction pathways.

Pushing the heterometal doping limit while preserving long-lived charge separation in a Ti-based MOF photocatalyst

This study explores the nature, dynamics, and reactivity of the photo-induced charge separated excited state in a Fe3+-doped titanium-based metal organic framework (MOF), xFeMIL125-NH2, as a function of iron concentration. The MOF is synthesized with doping levels x = 0.5, 1 and 2 Fe node sites per octameric Ti-oxo cluster and characterized by powder x-ray diffraction, UV-vis diffuse reflectance, atomic absorption, and steady state Fe K-edge X-ray absorption spectroscopy. For each doping level, time-resolved X-ray transient absorption spectroscopy studies confirm the electron trap site role of the Fe sites in the excited state. Time scan data reveal multiexponential decay kinetics for the charge recombination processes which extend into the microsecond range for all three concentrations. A series of dye photodegradation studies, based on the oxidative decomposition of Rhodamine B, demonstrates the reactivity of the charge separated excited state and the photocatalytic capacity of these MOF materials compared to traditional heterometal-doped semiconductor photocatalysts.

Surface plasmon resonance Bismuth-modified NH2-UiO-66 with enhanced photocatalytic tetracycline degradation performance

For nearly a century, the misuse of antibiotics has gradually polluted water and threatened human health. Photocatalysis is considered an efficient way to remove antibiotics from water. Zirconium-based metal–organic frameworks have attracted much attention as promising photocatalysts for the degradation of antibiotics. However, single Zirconium-based metal–organic frameworks can still not achieve a more satisfactory photocatalytic efficiency, due to poor light absorption and charge separation efficiency. In this study, a novel metal-loaded metal–organic frameworks material was explored. As a potential photocatalytic material, the performance of NH2-UiO-66 in the photocatalytic degradation of tetracycline was greatly improved just by the loading of a single metal. Bismuth/NH2-UiO-66 photocatalysts of various compositions were physicochemically (TEM, SEM, XRD, XPS, BET, FTIR, UV–VIS, PL), and electrochemically (electrochemical impedance spectroscopy, photocurrent response) characterized. We evaluated the photocatalytic performance of Bismuth/NH2-UiO-66 composites by measuring their ability towards tetracycline decomposition in simulated sunlight irradiation conditions. The experimental results indicated that the introduction of metal Bismuth significantly boosts the photocatalytic activity of the composite catalysts. The final degradation rate of Bismuth/NH2-UiO-66 for tetracycline was found to be 95.8%, namely 2.7 times higher than pure NH2-UiO-66. This behavior is due to the surface plasmon resonance effect of Bismuth, which ameliorates the photocatalyst's electron-hole separation and strengthens the charge transfer. Apart from that, the presence of Bismuth magnifies the visible-light absorption range of Bismuth/NH2-UiO-66. In this study, an innovative approach for designing efficient and cost-effective metal-modified metal–organic frameworks photocatalysts is proposed.