MOF-based Composite Materials Research Articles

Metal-organic frameworks (MOFs) for photoreduction of CO2

In recent decades, human industrialisation has become increasingly advanced, and the quality of life has also improved. Subsequently, the excessive consumption of fossil fuels has caused a series of problems, for example, global environmental warming caused by excessive CO2 emissions. Among numerous CO2 reduction technologies, using solar energy as an energy source for the CO2 photoreduction is considered one of the most prospective technologies. This method not only reduces the amount of CO2, but also enables to converse CO2 into other valuable chemicals, thereby achieving carbon cycling. Metal-organic frameworks (MOFs) are composed of metal ions and organic ligands as three-dimensional porous materials. MOFs have many advantages, including sizeable specific surface area, excellent CO2 absorption capacity and modifiable pore structure, leading to broad application potential in photocatalytic reduction of CO2. This article mainly introduces three aspects: functionalisation and modification of pure MOFs, MOF-based composite materials, and MOF-derived materials, which further improve the CO2 photocatalytic efficiency of MOFs. Furthermore, it includes the analysis of reported examples, discussion and outlook on reaction mechanisms and challenges. At present, the main difficulties faced by MOFs-based photocatalysts lie in their economic feasibility and poor material stability. Therefore, this review aims to help stimulate in-depth research in this area as well as better exert the advantages of MOFs.

Stable ionic liquid/Zr-MOF co-modified silica microspheres: Facile construction strategy and promising chromatographic applications

The stability of porous metal-organic frameworks (MOFs) as ideal materials for adsorption and separation has always been a key concern. In this study, an ionic liquid (IL) with excellent properties synthesized under solvent-free conditions was used to modify Zr-MOF@SiO2 for the first time to enhance the stability and improve the separation ability of Zr-MOF@SiO2 for chromatographic applications. The IL serves a dual purpose of supporting the backbone structure of Zr-MOF and acting as a ligand to coordinate with Zr(IV). This facile construction strategy ensures that the overall structural framework of the IL/Zr-MOF composite is more stable. Additionally, the presence of IL with imidazolium and carboxyl groups can facilitate efficient chromatographic separation by providing multiple interaction mechanisms. The results shows that the separation performance of the IL/Zr-MOF composite is significantly superior to that of the original Zr-MOF. Furthermore, the obtained new IL/Zr-MOF@SiO2 column exhibits appreciable stability, repeatability and reproducibility, which also performs well in the analysis of real samples with no significant matrix effects, demonstrating good reliability of the developed method. This study proposes a facile strategy for cleverly synthesizing a novel IL/Zr-MOF@SiO2 as an efficient chromatographic separation material, thereby potentially broadening the application of Zr-MOF in separation science. The facile preparation and promising application of IL/Zr-MOF may also offer a new possibility for employing MOF-based composite materials as effective liquid chromatographic stationary phases.

Research Progress in the Degradation of Chemical Warfare Agent Simulants Using Metal-Organic Frameworks.

Chemical warfare agents primarily comprise organophosphorus nerve agents, saliva alkaloids, cyanides, and mustard gas. Exposure to these agents can result in severe respiratory effects, including spasms, edema, and increased secretions leading to breathing difficulties and suffocation. Protecting public safety and national security from such threats has become an urgent priority. Porous metal-organic framework (MOF) materials have emerged as promising candidates for the degradation of chemical warfare agents due to their large surface area, tunable pore size distribution, and excellent catalytic performance. Furthermore, combining MOFs with polymers can enhance their elasticity and processability and improve their degradation performance. In this review, we summarize the literature of the past five years on MOF-based composite materials and their effectiveness in degrading chemical warfare agents. Moreover, we discuss key factors influencing their degradation efficiency, such as MOF structure, pore size, and functionalization strategies. Furthermore, we highlight recent developments in the design of MOF-polymer composites, which offer enhanced degradation performance and stability for practical applications in CWA degradation. These composite materials exhibit good performance in degrading chemical warfare agents, playing a crucial role in protecting public safety and maintaining national security. We can expect to see more breakthroughs in the application of metal-organic framework porous materials for degrading chemical warfare agents. It is hoped that these innovative materials will play a positive role in achieving social stability and security.

Facile fabrication of MOF-based composite membranes with liquid crystal ordered microstructure for effective dyes separation

High-performance membranes for effective dye/water separation are urgently desired in chemical industrial manufacture, and Metal-organic frameworks (MOFs) with abundant microporous structures are considered suitable candidates for fabricating separation membranes. However, for MOF-based membranes, maintaining superior separation efficiency while ensuring high water flux remains a challenge. In this study, a series of novel MOF-based composite materials (TFNs) and membranes oriented by electric fields (fio-TFNs) were fabricated using NH2-MIL-53(Fe), a thermotropic liquid crystal, poly (styrene-4-sulfonic acid), and polytetrafluoroethylene. The fio-TFN membranes exhibited characteristics of orientation and uniform distribution, and showed higher water flux and dye rejection compared with ordinary TFN membranes. This highlights the significant role played by the ordered orientation of liquid crystal molecules induced by the electric field in effective dye/water separation. High porosity is the basis of dye absorption, and the electrostatic interaction among structural charges and dyes is the dominant driving forces in these dye/water separation systems. The prepared fio-TFN membranes exhibited excellent performance in effective dye separation. For instance, the fio-TFN-1 membrane demonstrated high water flux (up to 255.9 L·m−2 h−1 bar−1) and excellent dye rejection rates (≥97 %, 92 %, and 82 % for methyl blue, congo red, and rhodamine B, respectively). Moreover, these prepared membranes exhibited excellent long-term stability, reusability, and flexibility, indicating their potential as high-performance separation membranes for wastewater treatment.

Integration of metal-organic frameworks and clay toward functional composite materials.

Metal-organic frameworks (MOFs) have become increasingly important as a class of porous crystalline materials because of their diverse applications. At the same time, significant progress has been achieved in the field of MOF-based composite materials toward novel applications based on the synergistic effect of two or more different components. Clay materials have been explored recently in MOF chemistry for the synthesis of MOF-clay composites, which are a new class of functional materials synthesized by a cooperative combination of MOFs with clay. Such composites have evolved only in the recent past with important functions and applications, such as enhanced gas storage and separation, CO2 capture and conversion, catalysis, drug delivery, and water harvesting. Notably, the typical shortcomings of MOFs, such as moisture sensitivity, poor water dispersibility, poor thermal and chemical stability, and poor processability, could be overcome by developing novel MOF-clay composites. This article provides a concise overview of MOF-clay composites and their applications in various fields that will drive the interest of researchers to explore the emerging field of MOF-clay chemistry. In the initial sections, we classify the clays that have been used in MOF chemistry and briefly discuss their structures and chemistry. We also present the advantages of MOF-clay composites and discuss their synthetic methodologies. In the later sections, we classify different MOF-clay composites based on the clay and present some representative examples of such composites that show unique properties and applications. Finally, the development in this field is summarized, and the future scope of such composites is discussed.

Fabrication of nanocomposite membrane based on post-synthetic modification of two-dimensional metal-organic framework nanosheet

• Post-synthetic modification of two-dimensional metal-organic framework. • CuBDC-NH 2 nanosheet reacts with isocyanate-terminated polyurethane oligomer(PU). • The CuBDC-NH 2 /PU is conducted to prepare functional nanocomposite membrane. • The CuBDC-NH 2 /PU membrane shows over 93.0% removal rate for dye removal. Two-dimensional metal-organic framework (2D MOF) nanosheet is becoming as an attractive type of 2D materials. And Post-synthetic modification (PSM) provides a powerful method to modify the structure of MOF without altering its crystal topology, which can generate functional MOFs not accessible from direct synthesis and improve the compatibility between MOFs and other components in MOF-based composite materials, especially in MOF/polymer composite. In this work, a facile method based on PSM of 2D MOF with polymers is conducted to prepare functional nanocomposite membrane. First, the amino-functioned 2D MOF nanosheet, CuBDC-NH 2 (BDC-NH 2 is 2-amino-1,4-benzenedicarboxylate), has been prepared as PSM precursor. Then CuBDC-NH 2 nanosheet reacts with isocyanate-terminated polyurethane (PU) oligomer through PSM to obtain CuBDC-NH 2 /PU nanocomposite membrane, which show over 93.0% removal rate for dye removal, such as methylene blue, Rhodamine B and Eosin Y.

Rod-shaped units based cobalt(II) organic framework as an efficient electrochemical sensor for uric acid detection in serum

Benefits from the unique [Co3(COO)4(μ3-O)2]n rod-shaped units and aromatic π-conjugated ligand, a 3D cobalt(II) organic framework was selected to explore its potential as a uric acid (UA) electrochemical sensor by coating onto the glassy carbon electrode (GCE). By utilizing electrocatalytic oxidation effects, the prepared modified electrode of 1/CB/GCE shows remarkable electrochemical sensing performances for detecting UA in PBS solution (pH = 7) with high sensitivity, high selectivity, good recyclability, and low detection limit of 3.4 ppb. This work demonstrates MOF-based composite materials have great potentials in clinical medicine, thereby providing a new way to design and develop electrochemical biosensors.

Leveraging Isothermal Titration Calorimetry to Obtain Thermodynamic Insights into the Binding Behavior and Formation of Metal-Organic Frameworks.

Isothermal titration calorimetry (ITC) is a technique which directly measures the thermodynamic parameters of binding events. Although historically it has been used to investigate interactions in biological macromolecules and the kinetics of enzyme-catalyzed reactions, ITC has also been demonstrated to provide relevant thermodynamic information about interactions in synthetic systems, such as those in metal-organic frameworks (MOFs). MOFs are a family of crystalline porous materials that have been widely studied as supports for molecules ranging from gases to biomolecules through physisorption and chemisorption. Herein, we offer a perspective on the current applications of ITC in MOFs, including the mechanism of small molecule adsorption and the formation of MOF-based composite materials through noncovalent interactions. Experimental considerations specific to running ITC experiments in MOF systems are reviewed on the basis of existing reports. We conclude by discussing underexplored, but promising, MOF-related research directions which could be elucidated by ITC.

3D Printing of Metal-Organic Framework-Based Ionogels: Wearable Sensors with Colorimetric and Mechanical Responses.

Soft ionotronics are emerging materials as wearable sensors for monitoring physiological signals, sensing environmental hazards, and bridging the human-machine interface. However, the next generation of wearable sensors requires multiple sensing capabilities, mechanical toughness, and 3D printability. In this study, a metal-organic framework (MOF) and three-dimensional (3D) printing were integrated for the synthesis of a tough MOF-based ionogel (MIG) for colorimetric and mechanical sensing. The ink for 3D printing contained deep eutectic solvents (DESs), cellulose nanocrystals (CNCs), MOF crystals, and acrylamide. After printing, further photopolymerization resulted in a second covalently cross-linked poly(acrylamide) network and solidification of MIG. As a porphyrinic Zr-based MOF, MOF-525 served as a functional filler to provide sharp color changes when exposed to acidic compounds. Notably, MOF-525 crystals also provided another design space to tune the printability and mechanical strength of MIG. In addition, the printed MIG exhibited high stability in the air because of the low volatility of DESs. Thereafter, wearable auxetic materials comprising MIG with negative Poisson's ratios were prepared by 3D printing for the detection of mechanical deformation. The resulting auxetic sensor exhibited high sensitivity via the change in resistance upon mechanical deformation and a conformal contact with skins to monitor various human body movements. These results demonstrate a facile strategy for the construction of multifunctional sensors and the shaping of MOF-based composite materials.

MOF-based composites for visible-light-driven heterogeneous photocatalysis: Synthesis, characterization and environmental application studies

The heterogeneous photocatalysis (HP), an advanced oxidation process that generates reactive oxygen species by activating a catalyst under irradiation, is considered one of the most viable treatment alternatives with various environmental applications. Thus, new visible-light active composite photocatalysts with a reduced e−−h+ ​recombination rate have been synthesized incorporationg metal-organic frameworks (MOFs) in semiconductors such as TiO2, ZnO, Fe2O3, Fe3O4, WO3, g-C3N4, RGO, and BiOBr for efficient and sustainable processes. MOFs have attracted much interest in the last years in the photocatalysis field due to their ordered crystalline structure, high porosity, and good optical response. Among the most described MOFs, MIL-n, UiO, and ZIF are notable interest families due to their excellent thermal stability and resistance to organic solvents and water. This review describes the characteristics, synthesis methods, and environmental applications of MOF-based composite materials as visible-light active catalysts. The photocatalytic results and potential applications of MOF-based composites for the degradation of organic compounds, Cr(VI) reduction, microorganisms inactivation, NOx oxidation, CO2 reduction, and H2 production are discussed, concluding with future perspectives.

Near-instantaneous catalytic hydrolysis of organophosphorus nerve agents with zirconium-based MOF/hydrogel composites

Zirconium-based metal-organic frameworks (Zr-MOFs) with Lewis-acidic sites are potent catalysts for degrading organophosphorus nerve agents. However, a volatile basic solution must regenerate the Zr-MOF catalysts, challenging its real-world implementation. By crosslinking polyethylene imine with an epoxide in the presence of selected Zr-MOFs, we prepared Zr-MOF/hydrogel composite catalysts for the rapid degradation of organophosphorus chemicals under atmospheric conditions. We developed a series of Zr-MOF hydrogel powder composites varying in Zr-node connectivity, linker functionality, and topology. The MOF-808 hydrogel powder was the highest-performing MOF-based composite for the hydrolysis of organophosphorus nerve-agent simulants. We coated the MOF-808 hydrogel onto a textile, and the composite rapidly detoxified nerve-agent simulants and actual nerve agents. The resulting half-lives are the fastest reaction rates to date among MOF-based composite materials, representing a critical step toward the production of protective gear for the instantaneous detoxification of nerve agents in practical conditions. • An amine-based hydrogel integrated with Zr-MOFs forms active detoxification catalysts • The MOF/hydrogel composites detoxify two organophosphorus nerve-agent simulants • The MOF/hydrogel composites integrated onto fiber detoxify GD and VX under ambient conditions Chemical warfare agents (CWAs) threaten the health and security of the global population, which motivates the development of protective wear that can rapidly detoxify CWAs into less-toxic species. Metal-organic frameworks (MOFs) are hybrid materials offering exceptional porosity and rich structural chemical diversity. The incorporation of Lewis-acidic sites into MOFs, specifically zirconium-based building blocks, forms highly active catalysts for the hydrolysis of organophosphorus nerve agents. However, a regenerating base and a source of water are needed, limiting the practical incorporation of Zr-MOFs in protective gear. To date, the subsequent incorporation of the active MOF onto a fiber composite has resulted in slow kinetics. Herein, we have designed a MOF/hydrogel powder and fibrous composites for the ultrafast solid-state catalytic detoxification of the phosphoester agents under ambient conditions. This scalable methodology is critical for realizing MOF-based protective masks and clothing. The development of heterogeneous catalyst composites that can detoxify organophosphorus chemical nerve agents through hydrolysis reactions is limited by slow kinetics and the need for water, as well as a base to regenerate the catalyst. We report the incorporation of an amine-based hydrogel integrated with Zr-MOFs onto a fibrous composite that results in the ultrafast solid-state catalytic detoxification of the phosphoester nerve agents (GD and VX) and their less-toxic chemical simulants under ambient conditions.

ZIF-8 Nanoparticles for Facile Processing into Useful Fabric Composites

Because of the importance of large-scale metal–organic framework (MOF) production and processing, the development of practical solutions to obtain commercially relevant MOF-based products is essential. Herein, we demonstrate a feasible pathway to construct functional zeolitic imidazolate framework-8 (ZIF-8)-coated fabric composite from commercially available precursors, through a scalable synthetic protocol to produce a large quantity of nanoscale ZIF-8, followed by a facile mean to drop-cast the powdered nanoparticles onto the fabric substrate. The ZIF-8/fabric composite shows enhanced organic dye adsorption capability and superior antibacterial property. This simple yet effective preparation process might be readily adopted for the large-scale production of useful MOF-based composite materials.

A new strategy for the preparation of core-shell MOF/Polymer composite material as the mixed-mode stationary phase for hydrophilic interaction/ reversed-phase chromatography

A facile method for efficient synthesis of core-shell composite material was proposed. In this method, the silica microspheres were co-modified with metal organic framework (MOF-235) and polyethylene glycol polymer (PEG) and used as mixed-mode stationary phase (MOF-235@PEG@silica) for high-performance liquid chromatography. Elemental analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and Brunauer-Emmett-Teller etc. methods were used to investigate the properties of the core-shell composite material. The MOF-235@PEG@silica stationary phase showed flexible selectivity for the separation of both hydrophilic and hydrophobic compounds especially for the separation of nine alkaloids, which showed superior hydrophilic separation performance than previous MOF-based composite stationary phases. Some factors including the pH of buffer salt, the ratio of organic phase and water phase in the mobile phase have been investigated, suggesting that the chromatographic retention mechanism of the column was a mixed mode of hydrophilic and reversed phase. The composite material also showed excellent chromatographic repeatability with the RSDs of the retention time found to be 0.2%–0.6% (n = 10) and the standard addition test in the actual sample proved that it can be used for practical sample analysis. In short, it provided a general way for preparing MOFs-based composites as mixed-mode chromatographic stationary phases, and changed the current status of MOF-based composite materials as single mode chromatographic stationary phases.

Tunable colors and white-light emissions by encapsulation of guest molecules or ions into a flexible metal–organic framework

Abstract Metal-organic frameworks (MOFs) are well known for their tunable structure and porosity with various important applications. In particular, their performance can be further improved by encapsulating luminescent guest molecules or lanthanide ions. This work aims to develop tunable colors and white-light emission materials by encapsulation of organic molecules and Eu3+ (or Tb3+) ions within a porous MOF (USTC-1). Various guest organic molecules or lanthanide ions are encapsulated into this MOF, yielding blue, blue-green, green, pink and red phosphorescence, respectively. Significantly, white-light emission can be achieved by encapsulating yellow- or green/red-emitting guest organic molecule into blue-emissive USTC-1 and adjusting the content of guest organic molecules. In addition, the white-light emissive USTC-1 composite materials can also be easily achieved by variation of the inclusion amount of single Eu3+ or Tb3+ ion in the host framework of USTC-1. The present work firstly reported white-light MOF-based composite materials by encapsulation of single organic molecule (non-dye molecule), and such strategy may open new perspectives for developing novel white-light emission materials by encapsulation of organic molecules or lanthanide ions.

High-performance asymmetric supercapacitor made of NiMoO4 nanorods@Co3O4 on a cellulose-based carbon aerogel.

In this study, a new nanoporous material comprising NiMoO4 nanorods and Co3O4 nanoparticles derived from ZIF-67 supported by a cellulose-based carbon aerogel (CA) has been successfully synthesized using a two-step hydrothermal method. Due to its chemical composition, the large specific surface and the hierarchical porous structure, the NiMoO4@Co3O4/CA ternary composite yields electrodes with an enhanced specific capacitance of 436.9 C/g at a current density of 0.5 A/g and an excellent rate capability of 70.7% capacitance retention at 5.0 A/g. Moreover, an advanced asymmetric supercapacitor (ASC) is assembled using the NiMoO4@Co3O4/CA ternary composite as the positive electrode and activated carbon as the negative electrode. The ASC device exhibits a large capacitance of 125.4 F/g at 0.5 A/g, a maximum energy density of 34.1 Wh/kg at a power density of 208.8 W/kg as well as a good cyclic stability (84% after 2000 cycles), indicating its wide applicability in energy storage. Finally, our results provide a general approach to the construction of CA and MOF-based composite materials with hierarchical porous structure for potential applications in supercapacitors.

Two dimensional metal-organic frameworks-derived leaf-like Co4S3/CdS composite for enhancing photocatalytic water evolution

The two dimensional (2D) lamellar structure materials with micron length of lateral can offer abundant reactive sites, high surface area and high flexibility for separating the photo-induced electron-hole pairs, and the obtained nanosheets possess tremendous potential to achieve efficient photocatalytic performance. Herein, we design and successfully synthesize 2D MOF-derived leaf-like structured Co4S3 decorated with CdS photocatalyst by a facile method, which possesses a lateral size of 3–6 μm with the thickness of 130–160 nm. The maximum optical absorption wavelength of Co4S3/CdS extends remarkably from 570 nm to 720 nm in visible light region compared with pure CdS nanospheres, demonstrating that the Co4S3/CdS hybrid material has higher solar energy utilization efficiency. Benefited from the structural advantages and the improvement of the absorption region, the optimized Co4S3/CdS (0.2) exhibits superior hydrogen production performance, and the amount of H2 reaches 5892.6 μmol h−1 g−1 under continuous visible-light illumination. Notably, the result manifests over 6 times greater than the neat CdS nanoparticles. Above all, this work provides a remarkable stepping stone in rationally constructing 2D MOF-based composite materials for sustainable energy sources applied in the field of photocatalytic hydrogen evolution.

Anchoring metal-organic framework nanoparticles on graphitic carbon nitrides for solar-driven photocatalytic hydrogen evolution

The development of low-cost and noble metal-free photocatalytic materials with precisely controlled morphologies and interfaces is vital to achieving highly efficient solar-to-fuel conversion. We herein report the fabrication of novel metal-organic framework (MOF)/g-C3N4 heterostructured materials with well-defined micro-/nanostructures and intimate interfacial contact. Zeolitic imidazolate framework-8 (ZIF-8) nanoparticles are found to be evenly anchored on modified rod-like g-C3N4 materials. The resultant hybrid materials demonstrate the integration of two components and show enhanced light-harvesting property in the visible light region. ZIF-8/g-C3N4 composite materials have been employed as the catalysts for solar-driven photocatalytic hydrogen evolution from water splitting. Under light emitting diode (LED) illumination, ZIF-8/g-C3N4 composite photocatalysts exhibit significant hydrogen-evolving performance in comparison to bulk ZIF-8 material. The enhanced hydrogen production efficiency can be ascribed to synergistic improvements in electron-hole separation, charge transportation and redox capability. This synthetic strategy can be extended to the design and controllable synthesis of a variety of MOF-based composite materials for energy and environmental applications.

One-Pot Synthesis of a Magnetic, Ratiometric Fluorescent Nanoprobe by Encapsulating Fe3O4 Magnetic Nanoparticles and Dual-Emissive Rhodamine B Modified Carbon Dots in Metal-Organic Framework for Enhanced HClO Sensing.

In this work, a new magnetic, ratiometric fluorescent nanoprobe has been designed and fabricated by encapsulating Fe3O4 magnetic nanoparticles (MNPs) and dual-emissive carbon dots into the cavities of metal-organic frameworks (MOFs). This one-pot method combined hybrid characteristics of MOFs with multiple properties of the encapsulated functional materials. The MOF-based nanoprobe possessed the advantages of MOFs (strong adsorption ability, accumulating the analytes), Fe3O4 MNPs (magnetic separation), and ratiometric sensors (eliminating the variabilities caused by the instability of the instruments and environment). The MOF-based nanoprobe was dispersible and stable in aqueous solution, and the nanoprobe was applied to HClO sensing. This work will provide a promising strategy for design and synthesis of novel MOF-based composite materials.

Metal–Organic Frameworks for Cell and Virus Biology: A Perspective

Metal-organic frameworks (MOFs) are a class of coordination polymers, consisting of metal ions or clusters linked together by chemically mutable organic groups. In contrast to zeolites and porous carbons, MOFs are constructed from a building block strategy that enables molecular level control of pore size/shape and functionality. An area of growing interest in MOF chemistry is the synthesis of MOF-based composite materials. Recent studies have shown that MOFs can be combined with biomacromolecules to generate novel biocomposites. In such materials, the MOF acts as a porous matrix that can encapsulate enzymes, oligonucleotides, or even more complex structures that are capable of replication/reproduction (i.e., viruses, bacteria, and eukaryotic cells). The synthetic approach for the preparation of these materials has been termed "biomimetic mineralization", as it mimics natural biomineralization processes that afford protective shells around living systems. In this Perspective, we focus on the preparation of MOF biocomposites that are composed of complex biological moieties such as viruses and cells and canvass the potential applications of this encapsulation strategy to cell biology and biotechnology.

CdS nanosphere-decorated hollow polyhedral ZCO derived from a metal-organic framework (MOF) for effective photocatalytic water evolution.

Semiconductor nanostructures have received considerable attention in the field of photocatalytic hydrogen evolution. However, eco-friendly, high efficiency, and low-cost semiconductor materials are still desired. In consideration of this, herein, we design a new and economic noble-metal-free CdS/ZnxCo3-xO4 (CdS/ZCO) nanohybrid photocatalyst using a metal-organic framework (MOF) template, which is a framework structure composed of organic ligands and metal ion nodes with different numbers of connections. The as-prepared CdS/ZCO composites with a large specific surface area and porous hollow structure exhibit remarkable catalytic activity and high stability for hydrogen generation. The hydrogen evolution rate is about 3978.6 μmol g-1 h-1 with lactic acid as the sacrificial agent when the optimized amount of CdS nanoparticles (30 wt%) is decorated on the ZCO frame, and the production efficiency of H2 for CdS/ZCO is 4 times higher than that for CdS nanospheres or CdS/Co3O4. The significantly enhanced photocatalytic activity of CdS/ZCO is attributed to the efficient charge separation and transfer between the phase boundary of CdS and ZCO. In addition, the composites exhibit better hydrogen production in lactic acid than in methanol, and the remarkable catalytic activity and high stability of the CdS/ZCO composites for hydrogen evolution indicate that MOF-based composite materials have potential application prospects in energy conversion.