In Situ Observation of Hot Carrier Transfer at Plasmonic Au/Metal-Organic Frameworks (MOFs) Interfaces

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal-organic frameworks (MOFs, NH₂−MIL-125 and MIL-125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon-excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti₈O₈(OH)₄ cluster) of the MOF structure, and the plasmon-excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4-benzenedicarboxylate−NH₂). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular-level manipulation of interface charge transfer on plasmonic photocatalysts.     

Photoactive Zr and Ti Metal-Organic-Frameworks for Solid-State Solar Cells

Solid-state photovoltaic cells based on robust metal-organic frameworks (MOFs), MIL-125(Ti), MIL-125(Ti)-NH₂, UiO-67, Ru(bpy)₂-UiO-67, (bpy 2,2‘-bipyridine) as active components and spiro-MeOTAD (MeOTAD 2,2‘,7,7‘-tetrakis[N,N-di(p-methoxyphenyl)amino]-9,9′-spirobifluorene) as hole transporting layer have been prepared., The photovoltaic response of this material increases in the presence of bathochromic −NH₂ groups on the linker or Ru (II) polypyridyl complexes light harvester. These results show that the strategies typically employed in photocatalysis to enhance the photocatalytic activity of MOFs can also be applied in the field of photovoltaic devices.     

On the limit of proton-coupled electronic doping in a Ti(iv)-containing MOF

Ti^IV-containing metal–organic frameworks are known to accumulate electrons in their conduction bands, accompanied by protons, when irradiated in the presence of alcohols. The archetypal system, MIL-125, was recently shown to reach a limit of 2e⁻ per Ti₈ octomeric node. However, the origin of this limit and the broader applicability of this unique chemistry relies not only on the presence of Ti^IV, but also access to inorganic inner-sphere Lewis basic anions in the MOF nodes. Here, we study the loading of protons and electrons in MIL-125, and assess the thermodynamic limit of doping these materials. We find that the limit is determined by the reduction potential of protons: in high charging regimes the MOF exceeds the H⁺/H₂ potential. Generally, we offer the design principle that inorganic anions in MOF nodes can host adatomic protons, which may stabilize meta-stable low valent transition metals. This approach highlights the unique chemistry afforded by MOFs built from inorganic clusters, and provides one avenue to developing novel catalytic scaffolds for hydrogen evolution and transfer hydrogenation.

Photo-promoted doping of MIL-125 is limited by the potential of MOF-bound protons exceeding the hydrogen evolution reaction.     

Enhanced Photocatalytic Activity of MIL‐125 by Post‐Synthetic Modification with CrIII and Ag Nanoparticles

NH₂‐MIL‐125, [Ti₈O₈(OH)₄(bdc‐NH₂)₆] (bdc^2?=1,4‐benzene dicarboxylate) is a highly porous metal–organic framework (MOF) that has a band gap lying within the ultraviolet region at about 2.6 eV. The band gap may be reduced by a suitable post‐synthetic modification of the nanochannels using conventional organic chemistry methods. Here, it is shown that the photocatalytic activity of NH₂‐MIL‐125 in the degradation of methylene blue under visible light is remarkably augmented by post‐synthetic modification with acetylacetone followed by Cr^III complexation. The latter metal ion extends the absorption from the ultraviolet to the visible light region (band gap 2.21 eV). The photogenerated holes migrate from the MOF’s valence band to the Cr^III valence band, promoting the separation of holes and electrons and increasing the recombination time. Moreover, it is shown that the MOF’s photocatalytic activity is also much improved by doping with Ag nanoparticles, formed in situ by the reduction of Ag⁺ with the acetylacetonate pendant groups (the resulting MOF band gap is 2.09 eV). Presumably, the Ag nanoparticles are able to accept the MOF’s photogenerated electrons, thus avoiding electron–hole recombination. Both, the Cr‐ and Ag‐bearing materials are stable under photocatalytic conditions. These findings open new avenues for improving the photocatalytic activity of MOFs.     

Design of Single‐Site Photocatalysts by Using Metal–Organic Frameworks as a Matrix

Single‐site photocatalysts generally display excellent photocatalytic activity and considerably high stability compared with homogeneous catalytic systems. A rational structural design of single‐site photocatalysts with isolated, uniform, and spatially separated active sites in a given solid is of prime importance to achieve high photocatalytic activity. Intense attention has been focused on the design and fabrication of single‐site photocatalysts by using porous materials as a platform. Metal–organic frameworks (MOFs) have great potential in the design and fabrication of single‐site photocatalysts due to their remarkable porosity, ultrahigh surface area, extraordinary tailorability, and significant diversity. MOFs can provide an abundant number of binding sites to anchor active sites, which results in a significant enhancement in photocatalytic performance. In this focus review, the development of single‐site MOF photocatalysts that perform important and challenging chemical redox reactions, such as photocatalytic H₂ production, photocatalytic CO₂ conversion, and organic transformations, is summarized thoroughly. Successful strategies for the construction of single‐site MOF photocatalysts are summarized and major challenges in their practical applications are noted.     

Photocatalytic Degradation of Dyes Using Titania Nanoparticles Supported in Metal-Organic Materials Based on Iron

Composite materials based on titania nanoparticles (TiO₂ NPs) and three metal-organic frameworks (MOFs) called MIL-53 (Fe) ((Fe (III) (OH) (1,4-BDC)), MILs (Materials Institute Lavoisier)), MIL-100 (Fe) (Fe₃O(H₂O)₂OH(BTC)₂), and Fe-BTC (iron-benzenetricarboxylate) with different percentages of TiO₂ NPs (0.5, 1, and 2.5% wt.) were synthesized using the solvothermal method and used as photocatalytic materials in the degradation of two dyes (Orange II and Reactive Black 5 (RB5)). The pristine and composite materials were characterized with X-ray diffraction, Raman, UV–Vis and Fourier transform infrared spectroscopy and scanning electron microscopy techniques. The 2.5TiO₂/MIL-100 composite material showed the best results for the degradation of both dyes (Reactive Black 5 and Orange II dye, 99% and 99.5% degradation in 105 and 150 min, respectively). The incorporation of TiO₂ NPs into MOFs can decrease the recombination of the change carrier in the MOF, increasing the photocatalytic activity of a pristine MOF. Results therefore indicated that the synthesized MOF nanocomposites have good potential for wastewater treatment.     

Studies on Photocatalytic CO2 Reduction over NH2‐Uio‐66(Zr) and Its Derivatives: Towards a Better Understanding of Photocatalysis on Metal–Organic Frameworks

Metal–organic framework (MOF) NH₂‐Uio‐66(Zr) exhibits photocatalytic activity for CO₂ reduction in the presence of triethanolamine as sacrificial agent under visible‐light irradiation. Photoinduced electron transfer from the excited 2‐aminoterephthalate (ATA) to Zr oxo clusters in NH₂‐Uio‐66(Zr) was for the first time revealed by photoluminescence studies. Generation of Zr^III and its involvement in photocatalytic CO₂ reduction was confirmed by ESR analysis. Moreover, NH₂‐Uio‐66(Zr) with mixed ATA and 2,5‐diaminoterephthalate (DTA) ligands was prepared and shown to exhibit higher performance for photocatalytic CO₂ reduction due to its enhanced light adsorption and increased adsorption of CO₂. This study provides a better understanding of photocatalytic CO₂ reduction over MOF‐based photocatalysts and also demonstrates the great potential of using MOFs as highly stable, molecularly tunable, and recyclable photocatalysts in CO₂ reduction.     

Criteria for Efficient Photocatalytic Water Splitting Revealed by Studying Carrier Dynamics in a Model Al-doped SrTiO3 Photocatalyst

Overall water splitting (OWS) using semiconductor photocatalysts is a promising method for solar fuel production. Achieving a high quantum efficiency is one of the most important prerequisites for photocatalysts to realize high solar-to-fuel efficiency. In a recent study (Nature 2020 , 58, 411–414), a quantum efficiency of almost 100 % has been achieved in an aluminum-doped strontium titanate (SrTiO₃ : Al) photocatalyst. Herein, using the SrTiO₃ : Al as a model photocatalyst, we reveal the criteria for efficient photocatalytic water splitting by investigating the carrier dynamics through a comprehensive photoluminescence study. It is found that the Al doping suppresses the generation of Ti³⁺ recombination centers in SrTiO₃, the surface band bending facilitates charge separation, and the in situ photo-deposited Rh/Cr₂O₃ and CoOOH co-catalysts render efficient charge extraction. By suppressing photocarrier recombination and establishing a facile charge separation and extraction mechanism, high quantum efficiency can be achieved even on photocatalysts with a very short (sub-ns) intrinsic photocarrier lifetime, challenging the belief that a long carrier lifetime is a fundamental requirement. Our findings could provide guidance on the design of OWS photocatalysts toward more efficient solar-to-fuel conversion.     

Post-modification of metal-organic framework for improved CO2 photoreduction efficiency

Utilizing metal-organic frameworks (MOFs) to design photocatalysts for CO₂ reduction catalysts is an excellent idea but currently restricted by the relatively low activity. Enhancing CO₂ affinity and tuning the oxidation state of metal clusters in MOFs might be a solution to improve the catalytic performance. Herein, the Cl-bridge atoms in the metal clusters of a cobalt MOF were easily exchanged with OH^?, which simultaneously oxidized a portion of Co(II) to Co(III) and resulted in a much enhanced photocatalytic activity for CO₂ reduction. In contrast, the original framework does not exhibit such superior activity. Comprehensive characterizations on their physicochemical properties revealed that the introduction of hydroxyl group not only greatly increases the CO₂ affinity but also alters the oxidation state of metal clusters, resulting in significantly improved photocatalytic activities for CO₂ reduction. This work provides important insight into the design of efficient photocatalysts.     

Noble Metals Can Have Different Effects on Photocatalysis Over Metal–Organic Frameworks (MOFs): A Case Study on M/NH2‐MIL‐125(Ti) (M=Pt and Au)

M‐doped NH₂‐MIL‐125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H₂ flow. The resultant samples were characterized by powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), X‐ray absorption fine structure (XAFS) analyses, N₂‐sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO₂ with triethanolamine (TEOA) as sacrificial agent under visible‐light irradiations showed that the noble metal‐doping on NH₂‐MIL‐125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH₂‐MIL‐125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt‐ and Au‐loaded NH₂‐MIL‐125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH₂‐MIL‐125(Ti), Pt/NH₂‐MIL‐125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH₂‐MIL‐125(Ti).The photocatalytic mechanisms over M/NH₂‐MIL‐125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH₂‐MIL‐125(Ti) and its promoting effect on the photocatalytic CO₂ reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH₂‐MIL‐125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal‐doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions.     

Experimental and Theoretical Study on the Interchange between Zr and Ti within the MIL-125-NH2 Metal Cluster

This study aims to investigate the effect of replacing Ti with Zr in the SBU of MIL-125-NH₂. We were able to replace Ti with Zr in the mixed metal synthesis of MIL-125-NH₂, for the first time. After experimentally confirming the consistency in their framework structure and comparing their morphology, we related the femtosecond light dynamics with photocatalytic CO₂ visible light conversion yield of the different variants in order to establish the composition-function relation in MIL-125 vis a vis CO₂ reduction. Introducing Zr to the system was found to cause structure defects due to missing linkers. The lifetime of the charge carriers for the mixed metal samples were shorter than that of the MIL-125-NH₂. The study of CO₂ photocatalytic reduction under visible light indicated that the NH₂ group enhances the photocatalytic activity while the Zr incorporation inside the MIL framework introduces no significant improvements. In addition, the material systems were modelled and simulated through DFT calculations which concluded that the decrease of the photocatalytic activity is not related to the system electronic structure, insinuating that defects are the culprit.     

Synthesis of W‐doped TiO2 by low‐temperature hydrolysis: Effects of annealing temperature and doping content on the surface microstructure and photocatalytic activity

A series of tungsten‐doped Titania photocatalysts were synthesized using a low‐temperature method. The effects of dopant concentration and annealing temperature on the phase transitions, crystallinity, electronic, optical, and photocatalytic properties of the resulting material were studied. The X‐ray patterns revealed that the doping delays the transition of anatase to rutile to a high temperature. A new phase W_yTi_1‐yO₂ appeared for 5.00 wt% W‐TiO₂ annealed at 900 °C. Raman and diffuse reflectance UV–Vis spectroscopy showed that band gap values decreased slightly up to 700 °C. X‐ray photoelectron spectroscopy showed that surface species viz. Ti³⁺, Ti⁴⁺, O^2?, oxygen‐vacancies, and adsorbed OH groups vary depending on the preparation conditions. The photocatalytic activity was evaluated via the degradation of methylene blue using LED white light. The degradation rate was affected by the percentage of dopants. The best photocatalytic activity was achieved with the sample labeled 5.00 wt% W‐TiO₂ annealed at 700 °C.     

Enhancing Built-in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C60 Fullerene into Zirconium-Based Metal-Organic Frameworks

High-efficiency photocatalysts based on metal-organic frameworks (MOFs) are often limited by poor charge separation and slow charge-transfer kinetics. Herein, a novel MOF photocatalyst is successfully constructed by encapsulating C₆₀ into a nano-sized zirconium-based MOF, NU-901. By virtue of host-guest interactions and uneven charge distribution, a substantial electrostatic potential difference is set-up in C₆₀@NU-901. The direct consequence is a robust built-in electric field, which tends to be 10.7 times higher in C₆₀@NU-901 than that found in NU-901. In the catalyst, photogenerated charge carriers are efficiently separated and transported to the surface. For example, photocatalytic hydrogen evolution reaches 22.3 mmol g⁻¹ h⁻¹ for C₆₀@NU-901, which is among the highest values for MOFs. Our concept of enhancing charge separation by harnessing host-guest interactions constitutes a promising strategy to design photocatalysts for efficient solar-to-chemical energy conversion.     

Amino-Functionalized Titanium Based Metal-Organic Framework for Photocatalytic Hydrogen Production

Photocatalytic hydrogen production using stable metal-organic frameworks (MOFs), especially the titanium-based MOFs (Ti-MOFs) as photocatalysts is one of the most promising solutions to solve the energy crisis. However, due to the high reactivity and harsh synthetic conditions, only a limited number of Ti-MOFs have been reported so far. Herein, we synthesized a new amino-functionalized Ti-MOFs, named NH₂-ZSTU-2 (ZSTU stands for Zhejiang Sci-Tech University), for photocatalytic hydrogen production under visible light irradiation. The NH₂-ZSTU-2 was synthesized by a facile solvothermal method, composed of 2,4,6-tri(4-carboxyphenylphenyl)-aniline (NH₂-BTB) triangular linker and infinite Ti-oxo chains. The structure and photoelectrochemical properties of NH₂-ZSTU-2 were fully studied by powder X-ray diffraction, scanning electron microscope, nitro sorption isotherms, solid-state diffuse reflectance absorption spectra, and Mott–Schottky measurements, etc., which conclude that NH₂-ZSTU-2 was favorable for photocatalytic hydrogen production. Benefitting from those structural features, NH₂-ZSTU-2 showed steady hydrogen production rate under visible light irradiation with average photocatalytic H₂ yields of 431.45 μmol·g⁻¹·h⁻¹ with triethanolamine and Pt as sacrificial agent and cocatalyst, respectively, which is almost 2.5 times higher than that of its counterpart ZSTU-2. The stability and proposed photocatalysis mechanism were also discussed. This work paves the way to design Ti-MOFs for photocatalysis.     

An Amine-Functionalized Zirconium Metal–Organic Polyhedron Photocatalyst with High Visible-Light Activity for Hydrogen Production

Metal–organic polyhedra (MOPs) are promising candidates for many potential applications; however, their use as photocatalysts for hydrogen production has yet to be developed. Herein, the photocatalytic performance of a water-stable Zr-MOP, ZrT-1-NH₂, was evaluated, for the first time, through photocatalytic hydrogen evolution under visible-light irradiation. ZrT-1-NH₂ shows clearly enhanced photocatalytic activity (510.42 μmol g⁻¹ h⁻¹) for hydrogen production, in comparison with that of other homogeneous crystalline materials. If platinum nanoparticles were introduced into the photocatalytic system, the hydrogen production efficiency of ZrT-1-NH₂ could be further improved. For ZrT-1-NH₂, the conspicuous improvement in photocatalysis can be attributed to efficient electron–hole separation, targeted electron transfer, and excellent recombination suppression. Furthermore, ZrT-1-NH₂ shows excellent stability during photocatalytic hydrogen evolution over five continuous runs. This work illustrates that MOP-based photocatalysts hold promise for broad applications in the domain of clean energy.     

Heteroatom-Doped Ag25 Nanoclusters Encapsulated in Metal–Organic Frameworks for Photocatalytic Hydrogen Production

Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light-induced instability and the difficulty of utilizing the photogenerated carriers for photocatalysis pose significant challenges. Here, MAg₂₄ (M=Ag, Pd, Pt, and Au) NCs doped with diverse single heteroatoms have been encapsulated in a metal–organic framework (MOF), UiO-66-NH₂, affording MAg₂₄@UiO-66-NH₂. Strikingly, compared with Ag₂₅@UiO-66-NH₂, the MAg₂₄@UiO-66-NH₂ doped with heteroatom exhibits much enhanced activity in photocatalytic hydrogen production, among which AuAg₂₄@UiO-66-NH₂ presents the best activity up to 3.6 mmol g⁻¹ h⁻¹, far superior to all other counterparts. Moreover, they display excellent photocatalytic recyclability and stability. X-ray photoelectron spectroscopy and ultrafast transient absorption spectroscopy demonstrate that MAg₂₄ NCs encapsulated into the MOF create a favorable charge transfer pathway, similar to a Z-scheme heterojunction, when exposed to visible light. This promotes charge separation, along with optimized Ag electronic state, which are responsible for the superior activity in photocatalytic hydrogen production.     

Construction of NH2-MIL-125(Ti) nanoplates modified Bi2WO6 microspheres with boosted visible-light photocatalytic activity

Photoactive metal–organic frameworks (MOFs) have proven to be a promising porous material in the field of catalysis. Controllable integration of these MOFs with inorganic semiconductor materials may endow new multifunctional hybrid materials with preferable photocatalytic properties. In this research, NH₂-MIL-125(Ti) nanoplates modified Bi₂WO₆ microspheres was prepared via a simple solvothermal method. The photocatalytic behaviors of the acquired catalysts was evaluated via the degradation of tetracycline hydrochloride (TC) under visible light. The experimental results showed that NH₂-MIL-125(Ti)/Bi₂WO₆ composites display higher photocatalytic activity than that of single Bi₂WO₆, and the ideal incorporation amount of NH₂-MIL-125(Ti) was around 5 wt%. The steady state fluorescence spectrum, transient photocurrents and electrochemical impedance spectroscopy verified that the introduction of NH₂-MIL-125(Ti) could accelerate the separation and transfer of photogenerated carriers and thus improve the photocatalytic activity of Bi₂WO₆. The photocatalytic mechanism was explored in detail. This work extends the knowledge of integrating MOFs with traditional photocatalysts to form new composite materials in the area of environmental purification.

     

Incorporating Transition-Metal Phosphides Into Metal-Organic Frameworks for Enhanced Photocatalysis

Metal-organic frameworks (MOFs) have been shown to be an excellent platform in photocatalysis. However, to suppress electron–hole recombination, a Pt cocatalyst is usually inevitable, especially in photocatalytic H₂ production, which greatly limits practical application. Herein, for the first time, monodisperse, small-size, and noble-metal-free transitional-metal phosphides (TMPs; for example, Ni₂P, Ni₁₂P₅), are incorporated into a representative MOF, UiO-66-NH₂, for photocatalytic H₂ production. Compared with the parent MOF and their physical mixture, both TMPs@MOF composites display significantly improved H₂ production rates. Thermodynamic and kinetic studies reveal that TMPs, behaving similar ability to Pt, greatly accelerate the linker-to-cluster charge transfer, promote charge separation, and reduce the activation energy of H₂ production. Significantly, the results indicate that Pt is thermodynamically favorable, yet Ni₂P is kinetically preferred for H₂ production, accounting for the higher activity of Ni₂P@UiO-66-NH₂ than Pt@UiO-66-NH₂.     

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors

Crystalline and porous covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H₂ evolution due to their long‐range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two‐dimensional (2D) COF with stable MOF. By covalently anchoring NH₂‐UiO‐66 onto the surface of TpPa‐1‐COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H₂ evolution under visible light irradiation. Especially, NH₂‐UiO‐66/TpPa‐1‐COF (4:6) exhibits the maximum photocatalytic H₂ evolution rate of 23.41 mmol g^?1 h^?1 (with the TOF of 402.36 h^?1), which is approximately 20 times higher than that of the parent TpPa‐1‐COF and the best performance photocatalyst for H₂ evolution among various MOF‐ and COF‐based photocatalysts.     

Thermal expansion-quench of nickel metal-organic framework into nanosheets for efficient visible light CO2 reduction

Metal-organic framework nanosheets (MOF NNs) offer potential opportunities for many applications,but an efficient strategy for the scalable preparation of few-layered two-dimensional (2D) MOF NNs are still a major challenge.Herein,we present an efficient top-down method for the synthesis of the Ni-BDC(Ni₂(OH)₂(1,4-BDC);1,4-BDC=1,4-benzenedicarboxylate) nanosheets utilizing a novel thermal expansionquench method of the flowerlike bulky MOFs in liquid N₂.The obtain...