From UV to Near‐Infrared Light‐Responsive Metal–Organic Framework Composites: Plasmon and Upconversion Enhanced Photocatalysis

The exploitation of photocatalysts that harvest solar spectrum as broad as possible remains a high‐priority target yet grand challenge. In this work, for the first time, metal–organic framework (MOF) composites are rationally fabricated to achieve broadband spectral response from UV to near‐infrared (NIR) region. In the core–shell structured upconversion nanoparticles (UCNPs)‐Pt@MOF/Au composites, the MOF is responsive to UV and a bit visible light, the plasmonic Au nanoparticles (NPs) accept visible light, whereas the UCNPs absorb NIR light to emit UV and visible light that are harvested by the MOF and Au once again. Moreover, the MOF not only facilitates the generation of “bare and clean” Au NPs on its surface and realizes the spatial separation for the Au and Pt NPs, but also provides necessary access for catalytic substrates/products to Pt active sites. As a result, the optimized composite exhibits excellent photocatalytic hydrogen production activity (280 µmol g^?1 h^?1) under simulated solar light, and the involved mechanism of photocatalytic H₂ production under UV, visible, and NIR irradiation is elucidated. Reportedly, this is an extremely rare study on photocatalytic H₂ production by light harvesting in all UV, visible, and NIR regions.     

The Effect of Materials Architecture in TiO2/MOF Composites on CO2 Photoreduction and Charge Transfer

CO₂ photoreduction to C₁/C₁₊ energized molecules is a key reaction of solar fuel technologies. Building heterojunctions can enhance photocatalysts performance, by facilitating charge transfer between two heterojunction phases. The material parameters that control this charge transfer remain unclear. Here, it is hypothesized that governing factors for CO₂ photoreduction in gas phase are: i) a large porosity to accumulate CO₂ molecules close to catalytic sites and ii) a high number of “points of contact” between the heterojunction components to enhance charge transfer. The former requirement can be met by using porous materials; the latter requirement by controlling the morphology of the heterojunction components. Hence, composites of titanium oxide or titanate and metal–organic framework (MOF), a highly porous material, are built. TiO₂ or titanate nanofibers are synthesized and MOF particles are grown on the fibers. All composites produce CO under UV–vis light, using H₂ as reducing agent. They are more active than their component materials, e.g., ≈9 times more active than titanate. The controlled composites morphology is confirmed and transient absorption spectroscopy highlights charge transfer between the composite components. It is demonstrated that electrons transfer from TiO₂ into the MOF, and holes from the MOF into TiO₂, as the MOF induces band bending in TiO₂.     

Formation of N‐Doped Carbon‐Coated ZnO/ZnCo2O4/CuCo2O4 Derived from a Polymetallic Metal–Organic Framework: Toward High‐Rate and Long‐Cycle‐Life Lithium Storage

Metal–organic frameworks (MOFs) are very promising self‐sacrificing templates for the large‐scale fabrication of new functional materials owing to their versatile functionalities and tunable porosities. Most conventional metal oxide electrodes derived from MOFs are limited by the low abundance of incorporated metal elements. This study reports a new strategy for the synthesis of multicomponent active metal oxides by the pyrolysis of polymetallic MOF precursors. A hollow N‐doped carbon‐coated ZnO/ZnCo₂O₄/CuCo₂O₄ nanohybrid is prepared by the thermal annealing of a polymetallic MOF with ammonium bicarbonate as a pore‐forming agent. This is the first report on the rational design and preparation of a hybrid composed of three active metal oxide components originating from MOF precursors. Interestingly, as a lithium‐ion battery anode, the developed electrode delivers a reversible capacity of 1742 mAh g^?1 after 500 cycles at a current density of 0.3 mA g^?1. Furthermore, the material shows large storage capacities (1009 and 667 mAh g^?1), even at high current flow (3 and 10 A g^?1). The remarkable high‐rate capability and outstanding long‐life cycling stability of the multidoped metal oxide benefits from the carbon‐coated integrated nanostructure with a hollow interior and the three active metal oxide components.     

Novel MOF‐Derived Co@N‐C Bifunctional Catalysts for Highly Efficient Zn–Air Batteries and Water Splitting

Metal–organic frameworks (MOFs) and MOF‐derived materials have recently attracted considerable interest as alternatives to noble‐metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N‐C materials (C‐MOF‐C2‐T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C‐MOF‐C2‐900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N‐doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO₂, respectively. Primary Zn–air batteries based on C‐MOF‐900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g_Zn^–1 under 10 mA cm^–2. Rechargeable Zn–air batteries based on C‐MOF‐C2‐900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm^–2), along with an excellent cycling stability with no increase in polarization even after 120 h – outperform their counterparts based on noble‐metal‐based air electrodes. The resultant rechargeable Zn–air batteries are used to efficiently power electrochemical water‐splitting systems, demonstrating promising potential as integrated green energy systems for practical applications.     

Magnetic Metal–Organic Frameworks: γ‐Fe2O3@MOFs via Confined In Situ Pyrolysis Method for Drug Delivery

A general one‐step in situ pyrolysis route for the construction of metal–organic frameworks encapsulating superparamagnetic γ‐Fe₂O₃ NPs dispersed in the confined cavities of MOFs homogeneously is described. The integration of γ‐Fe₂O₃ NPs or clusters into MOFs can endow these porous materials with superparamagnetic element. By the combination of the thermal stability of MOFs and pyrolysis of metal triacetylacetonate complex at matched conditions, the porous structure of MOFs are well maintained while the size‐induced superparamagnetic property of nano γ‐Fe₂O₃ is obtained. As a proof of concept, both the γ‐ Fe₂O₃@ZIF‐8 and γ‐Fe₂O₃@MIL‐53(Al) were successfully prepared, and the latter was chosen to demonstrate its potential drug delivery as a magnetic MOF.     

Multifunctional Metal–Organic Frameworks for Photocatalysis

Metal–organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO₂ reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world‐wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF‐involved solar‐to‐chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co‐catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated.     

Self‐Template‐Directed Metal–Organic Frameworks Network and the Derived Honeycomb‐Like Carbon Flakes via Confinement Pyrolysis

Metal–organic frameworks (MOFs) have become a research hotspot since they have been explored as convenient precursors for preparing various multifunctional nanomaterials. However, the preparation of MOF networks with controllable flake morphology in large scale is not realized yet. Herein, a self‐template strategy is developed to prepare MOF networks. In this work, layered double‐metal hydroxide (LDH) and other layered metal hydroxides are used not only as a scaffold but also as a self‐sacrificed metal source. After capturing the abundant metal cations identically from the LDH by the organic linkers, MOF networks are in situ formed. It is interesting that the MOF network‐derived carbon materials retain the flake morphology and exhibit a unique honeycomb‐like macroporous structure due to the confined shrinkage of the polyhedral facets. The overall properties of the carbon networks are adjustable according to the tailored metal compositions in LDH and the derived MOFs, which are desirable for target‐oriented applications as exemplified by the electrochemical application in supercapacitors.     

Flexible Metal–Organic Framework‐Based Mixed‐Matrix Membranes: A New Platform for H2S Sensors

Metal–organic framework (MOF)–polymer mixed‐matrix membranes (MMMs) have shown great potential and superior performance in gas separations. However, their sensing application has not been fully established yet. Herein, a rare example of using flexible MOF‐based MMMs as a fluorescent turn‐on sensor for the detection of hydrogen sulfide (H₂S) is reported. These MOF‐based MMMs are readily prepared by mixing a highly stable aluminum‐based nano‐MOF (Al‐MIL‐53‐NO₂) into poly(vinylidene fluoride) with high loadings up to 70%. Unlike the intrinsic fragility and poor processability of pure‐MOF membranes, these MMMs exhibit desirable flexibility and processability that are more suitable for practical sensing applications. The uniform distribution of Al‐MIL‐53‐NO₂ particles combined with the permanent pores of MOFs enable these MMMs to show good water permeation flux and consequently have a full contact between the analyte and MOFs. The developed MMM sensor (70% MOF loading) thus shows a highly remarkable detection selectivity and sensitivity for H₂S with an exceptionally low detection limit around 92.31 × 10^?9m , three orders of magnitude lower than the reported powder‐form MOFs. This work demonstrates that it is feasible to develop flexible luminescent MOF‐based MMMs as a novel platform for chemical sensing applications.     

Kinetic‐Controlled Formation of Bimetallic Metal–Organic Framework Hybrid Structures

Heterometallic metal–organic frameworks (MOFs) are constructed from two or more kinds of metal ions, while still remaining their original topologies. Due to distinct reaction kinetics during MOF formation, partial distribution of different metals within a single MOF crystal can lead to sophisticated heterogeneous nanostructures. Here, this study reports an investigation of reaction kinetics for different metal ions in a bimetallic MOF system, the ZIF‐8/67 (M(2‐mIM)₂, M = Zn for ZIF‐8, and Co for ZIF‐67, 2‐mIM = 2‐methylimidazole), by in situ optical method. Distinct kinetics of the two metals forming single‐component MOFs are revealed, and when both Co and Zn ions are present in the starting solution, homogeneous distributions of the two metals are only achieved at high Co/Zn ratio, while at low Co/Zn ratio concentration gradient from Co‐rich cores to Zn‐rich shells is observed. Further, by adding the two metals in sequence, more sophisticated structures are achieved. Specifically, when Co²⁺ is added first, ZIF‐67@ZIF‐8/67 core–shell nanocrystals are achieved with tunable core/shell thickness ratio depending on the time intervals; while when Zn²⁺ is added first, only agglomerates of irregular shape form due to the weak nucleation ability of Zn²⁺.     

Shape‐Defined Hollow Structural Co‐MOF‐74 and Metal Nanoparticles@Co‐MOF‐74 Composite through a Transformation Strategy for Enhanced Photocatalysis Performance

In recent years, metal–organic frameworks (MOFs) have received extensive interest because of the diversity of their composition, structure, and function. To promote the MOFs' function and performance, the construction of hollow structural metal–organic frameworks and nanoparticle–MOF composites is significantly effective but remains a considerable challenge. In this article, a transformation strategy is developed to synthesize hollow structural Co‐MOF‐74 by solvothermal transformation of ZIF‐67. These Co‐MOF‐74 particles exhibit a double‐layer hollow shell structure without remarkable shape change compared to original ZIF‐67 particles. The formation of hollow structure stemmed from the density difference of Co between ZIF‐67 and Co‐MOF‐74. By this strategy, hollow structural Co‐MOF‐74 with different sizes and shapes are obtained from corresponding ZIF‐67, and metal nanoparticles@Co‐MOF‐74 is synthesized by corresponding nanoparticles@Co‐ZIF‐67. To verify the structural advantages of hollow structural Co‐MOF‐74 and Ag nanoparticles@Co‐MOF‐74, photocatalytic CO₂ reduction is used as a model reaction. Conventionally synthesized Co‐MOF‐74 (MOF‐74‐C), hollow structural Co‐MOF‐74 synthesized by transformation method (MOF‐74‐T) and Ag nanoparticles@Co‐MOF‐74 (AgNPs@MOF‐74) are used as cocatalysts in this reaction. As a result, the cocatalytic activity of MOF‐74‐T and AgNPs@MOF‐74 is 1.8 times and 3.8 times that of MOF‐74‐C, respectively.     

Guest-Induced Multilevel Charge Transport Strategy for Developing Metal-Organic Frameworks to Boost Photocatalytic CO2 Reduction

Encapsulating photogenerated charge-hopping nodes and space transport bridges within metal–organic frameworks (MOFs) is a promising method of boosting the photocatalytic performance. Herein, this work embeds electron transfer media (9,10-bis(4-pyridyl)anthracene (BPAN)) in MOF cavities to build multi-level electron transfer paths. The MOF cavities are accurately regulated to investigate the significance of the multi-level electron transfer paths in the process of CO₂ photoreduction by evaluating the difference in the number of guest media. The prepared MOFs, {[Co(BPAN)(1,4-dicarboxybenzene)(H₂O)₂]·BPAN·2H₂O} and {[Co(BPAN)₂(4,4′-biphenyldicarboxylic acid)₂(H₂O)₂]·2BPAN·2H₂O} (denoted as BPAN-Co-1 and BPAN-Co-2), exhibit efficient visible-light-driven CO₂ conversion properties. The CO photoreduction efficacy of BPAN-Co-2 (5598 µmol g⁻¹ h⁻¹) is superior to that of most reported MOF-based catalysts. In addition, the enhanced CO₂ photoreduction ability is supported by density functional theory (DFT). This work illustrates the feasibility of realizing charge separation characteristics in MOF catalysts at the molecular level, and provides new insight for designing high-performance MOFs for artificial photosynthesis.     

Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion

A highly porous metal‐organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn₂(COO)₄) and tetrameric (Zn₄(O)(CO₂)₆), is successfully assembled by the reaction of a tricarboxylate ligand with Zn^II ion. Subsequently, single‐crystal‐to‐single‐crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu^II and Co^II ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation‐exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu^II and Co^II exchanged samples exhibit comparable CO₂ adsorption capability to the pristine Zn^II‐based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO₂ with epoxides into related carbonates demonstrate that Zn^II‐based MOF affords the highest catalytic activity as compared with Cu^II and Co^II exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO₂ to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs.     

Ambient Fast Synthesis and Active Sites Deciphering of Hierarchical Foam‐Like Trimetal–Organic Framework Nanostructures as a Platform for Highly Efficient Oxygen Evolution Electrocatalysis

Metal–organic frameworks (MOFs) have attracted tremendous interest due to their promising applications including electrocatalysis originating from their unique structural features. However, it remains a challenge to directly use MOFs for oxygen electrocatalysis because it is quite difficult to manipulate their dimension, composition, and morphology of the MOFs with abundant active sites. Here, a facile ambient temperature synthesis of unique NiCoFe‐based trimetallic MOF nanostructures with foam‐like architecture is reported, which exhibit extraordinary oxygen evolution reaction (OER) activity as directly used catalyst in alkaline condition. Specifically, the (Ni₂Co₁)_0.925Fe_0.075‐MOF‐NF delivers a minimum overpotential of 257 mV to reach the current density of 10 mA cm^?2 with a small Tafel slope of 41.3 mV dec^?1 and exhibits high durability after long‐term testing. More importantly, the deciphering of the possible origination of the high activity is performed through the characterization of the intermediates during the OER process, where the electrochemically transformed metal hydroxides and oxyhydroxides are confirmed as the active species.     

Specific K+ Binding Sites as CO2 Traps in a Porous MOF for Enhanced CO2 Selective Sorption

Metal–organic frameworks (MOFs) can be fine‐tuned to boost sorbent‐sorbate interactions in order to improve gas sorption and separation performance, but the design of MOFs with ideal structural features for gas separation applications remains a challenge. Herein it is reported that unsaturated alkali metal sites can be immobilized in MOFs through a tetrazole based motif and that gas affinity can thereby be boosted. In the prototypal MOF of this type‐ NKU‐521 (NKU denotes Nankai University), K⁺ cations are effectively embedded in a trinuclear Co²⁺‐tetrazole coordination motif. The embedded K⁺ sites are exposed to the pores of NKU‐521 through water removal, and the isosteric heat (Q_st) for CO₂ is boosted to 41 kJ mol^‐1. The nature of the binding site is validated by molecular simulations and structural characterization. The K⁺ cations in effect serve as gas traps and boost the CO₂‐framework affinity, as measured by the Q_st, by 24%. In addition, the impact of unsaturated alkali metal sites upon the separation of hydrocarbons is evaluated for the first time in MOFs using ideal adsorbed solution theory (IAST) calculations and column breakthrough experiments. The results reveal that the presence of exposed K⁺ sites benefits gas sorption and hydrocarbon separation performances of this MOF.     

MOF‐Derived Metal Oxide Composites for Advanced Electrochemical Energy Storage

Over the past two decades, metal–organic frameworks (MOFs), a type of porous material, have aroused great interest as precursors or templates for the derivation of metal oxides and composites for the next generation of electrochemical energy storage applications owing to their high specific surface areas, controllable structures, and adjustable pore sizes. The electrode materials, which affect the performance in practical applications, are pivotal components of batteries and supercapacitors. Metal oxide composites derived from metal–organic frameworks possessing high reversible capacity and superior rate and cycle performance are excellent electrode materials. In this Review, potential applications for MOF‐derived metal oxide composites for lithium‐ion batteries, sodium‐ion batteries, lithium–oxygen batteries, and supercapacitors are studied and summarized. Finally, the challenges and opportunities for future research on MOF‐derived metal oxide composites are proposed on the basis of academic knowledge from the reported literature as well as from experimental experience.     

Super‐Stable,Highly Efficient,and Recyclable Fibrous Metal–Organic Framework Membranes for Precious Metal Recovery from Strong Acidic Solutions

Precious metals such as palladium (Pd) and platinum (Pt) are marvelous materials in the fields of electronic and catalysis, but they are tapering day by day. Zr(IV)‐based metal–organic frameworks (MOFs) are competent for their recovery, notably in harsh environments, while the general powder form limits their practical application. Porous MOF‐based membranes with ultraefficient metal ion permeation, strong stability, and high selectivity are, therefore, strikingly preferred. Herein, a set of polymeric fibrous membranes incorporated with the UiO‐66 series are fabricated; their adsorption/desorption capabilities toward Pd(II) and Pt(IV) are evaluated from strongly acidic solutions; and the MOF–polymer compatibilities are investigated. Polyurethane (PU)/UiO‐66‐NH₂ showed strong acid resistance and high chemical stability, which are attributable to strong π–π interactions between PU and MOF nanoparticles with a high configuration of energy. The as‐fabricated MOF membranes show extremely good adsorption/desorption performances without ruptures/coalitions of nanofibers or leak of MOF nanoparticles, and successfully display the efficacy in a gravity‐driven or even continuous‐flow system with good recycle performance and selectivity. The as‐fabricated MOF membranes set an example of potential MOF–polymer compatibility for practical applications.     

2D Metal–Organic Frameworks (MOFs) for High‐Performance BatCap Hybrid Devices

Two identical layered metal–organic frameworks (MOFs) (CoFRS and NiFRS) are constructed by using flexible 1,10‐bis(1,2,4‐triazol‐1‐yl)decane as pillars and 1,4‐benzenedicarboxylic acid as rigid linkers. The single‐crystal structure analysis indicates that the as‐synthesized MOFs possess fluctuant 2D networks with large interlayer lattices. Serving as active electrode elements in supercapacitors, both MOFs deliver excellent rate capabilities, high capacities, and longstanding endurances. Moreover, the new intermediates in two electrodes before and after long‐lifespan cycling are also examined, which cannot be identified as metal hydroxides in the peer reports. After assembled into battery‐supercapacitor (BatCap) hybrid devices, the NiFRS//activated carbon (AC) device displays better electrochemical results in terms of gravimetric capacitance and cycling performance than CoFRS//AC devices, and a higher energy‐density value of 28.7 Wh kg^?1 compared to other peer references with MOFs‐based electrodes. Furthermore, the possible factors to support the distinct performances are discussed and analyzed.     

DNA‐Assembled Core‐Satellite Upconverting‐Metal–Organic Framework Nanoparticle Superstructures for Efficient Photodynamic Therapy

DNA‐mediated assembly of core–satellite structures composed of Zr(IV)‐based porphyrinic metal‐organic framework (MOF) and NaYF₄,Yb,Er upconverting nanoparticles (UCNPs) for photodynamic therapy (PDT) is reported. MOF NPs generate singlet oxygen (¹O₂) upon photoirradiation with visible light without the need for additional small molecule, diffusional photosensitizers such as porphyrins. Using DNA as a templating agent, well‐defined MOF–UCNP clusters are produced where UCNPs are spatially organized around a centrally located MOF NP. Under NIR irradiation, visible light emitted from the UCNPs is absorbed by the core MOF NP to produce ¹O₂ at significantly greater amounts than what can be produced from simply mixing UCNPs and MOF NPs. The MOF–UCNP core–satellite superstructures also induce strong cell cytotoxicity against cancer cells, which are further enhanced by attaching epidermal growth factor receptor targeting affibodies to the PDT clusters, highlighting their promise as theranostic photodynamic agents.     

A Hydrangea‐Like Superstructure of Open Carbon Cages with Hierarchical Porosity and Highly Active Metal Sites

Carbon micro‐/nanocages have attracted great attention owing to their wide potential applications. Herein, a self‐templated strategy is presented for the synthesis of a hydrangea‐like superstructure of open carbon cages through morphology‐controlled thermal transformation of core@shell metal–organic frameworks (MOFs). Direct pyrolysis of core@shell zinc (Zn)@cobalt (Co)‐MOFs produces well‐defined open‐wall nitrogen‐doped carbon cages. By introducing guest iron (Fe) ions into the core@shell MOF precursor, the open carbon cages are self‐assembled into a hydrangea‐like 3D superstructure interconnected by carbon nanotubes, which are grown in situ on the Fe–Co alloy nanoparticles formed during the pyrolysis of Fe‐introduced Zn@Co‐MOFs. Taking advantage of such hierarchically porous superstructures with excellent accessibility, synergetic effects between the Fe and the Co, and the presence of catalytically active sites of both metal nanoparticles and metal–N_x species, this superstructure of open carbon cages exhibits efficient bifunctional catalysis for both oxygen evolution reaction and oxygen reduction reaction, achieving a great performance in Zn–air batteries.     

MOF‐Derived Bifunctional Cu3P Nanoparticles Coated by a N,P‐Codoped Carbon Shell for Hydrogen Evolution and Oxygen Reduction

Metal–organic frameworks (MOFs) have recently emerged as a type of uniformly and periodically atom‐distributed precursor and efficient self‐sacrificial template to fabricate hierarchical porous‐carbon‐related nanostructured functional materials. For the first time, a Cu‐based MOF, i.e., Cu‐NPMOF is used, whose linkers contain nitrogen and phosphorus heteroatoms, as a single precursor and template to prepare novel Cu₃P nanoparticles (NPs) coated by a N,P‐codoped carbon shell that is extended to a hierarchical porous carbon matrix with identical uniform N and P doping (termed Cu₃P@NPPC) as an electrocatalyst. Cu₃P@NPPC demonstrates outstanding activity for both the hydrogen evolution and oxygen reduction reaction, representing the first example of a Cu₃P‐based bifunctional catalyst for energy‐conversion reactions. The high performances are ascribed to the high specific surface area, the synergistic effects of the Cu₃P NPs with intrinsic activity, the protection of the carbon shell, and the hierarchical porous carbon matrix doped by multiheteroatoms. This strategy of using a diverse MOF as a structural and compositional material to create a new multifunctional composite/hybrid may expand the opportunities to explore highly efficient and robust non‐noble‐metal catalysts for energy‐conversion reactions.