Evidence of Photoinduced Charge Separation in the Metal–Organic Framework MIL‐125(Ti)‐NH2

Herein, we describe the photochemical behavior of the porous metal–organic framework MIL‐125(Ti)‐NH₂, built up from cyclic Ti₈O₈(OH)₄ oxoclusters and 2‐aminoterephthalate ligands. While MIL‐125(Ti)‐NH₂ does not emit upon excitation at 420 nm, laser flash photolyses of dry samples (diffuse reflectance) or aqueous suspensions (transmission) of the solid have allowed detecting a transient characterized by a continuous absorption from 390 to 820 nm decaying in the sub‐millisecond timescale, which is quenched by oxygen. This transient has been attributed to the charge‐separation state. Firm evidence for this assignment was obtained by lamp irradiation of aqueous suspensions of MIL‐125(Ti)‐NH₂ in the presence of electron‐donor (N,N,N′N′‐tetramethyl‐p‐phenylenediamine) or electron‐acceptor (methylviologen) probe molecules, which has allowed the visual detection of the corresponding radical ions, in agreement with the occurrence of photoinduced charge separation in MIL‐125(Ti)‐NH₂.     

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.     

Visible‐light photocatalytic activity of Ag@MIL‐125(Ti) microspheres

Ag nanoparticle (NP)‐decorated MIL‐125(Ti) microspheres (Ag@MIL‐125(Ti)) were firstly fabricated via a facile hydrothermal and following photo‐reduction method. The photocatalysts were characterized using X‐ray diffraction, scanning and transmission electron microscopies, X‐ray photoelectron spectroscopy and UV–visible diffuse reflectance spectroscopy. The characterization results indicated that Ag NPs were dispersed on the surface of MIL‐125(Ti) microspheres, and the Ag NPs had a uniform diameter of about 40 nm. The composites exhibited excellent visible‐light absorption, due to the modification with the Ag NPs. The photocatalytic activity for the visible‐light‐promoted degradation of Rhodamine B was improved through the optimization of the amount of Ag loaded as a co‐catalyst, this amount being determined as 3 wt%. Additionally, studies performed using radical scavengers indicated that O₂^? and e^? served as the main reactive species. The catalyst can be reused at least five times without significant loss of its catalytic activity. Furthermore, a photocatalytic mechanism for degradation of organics over Ag@MIL‐125(Ti) is also proposed. Copyright © 2015 John Wiley & Sons, Ltd.     

Metal–organic framework MIL‐125(Ti) for efficient adsorptive removal of Rhodamine B from aqueous solution

A metal–organic framework material, MIL‐125(Ti), was solvothermally prepared and characterized using X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy and surface area measurements. MIL‐125(Ti) was then used as an adsorbent for Rhodamine B (RhB) removal in aqueous solution. The adsorption kinetics, adsorption mechanism, adsorption isotherm, activation energy and various thermodynamic parameters were studied in detail. The maximum adsorption capacity of MIL‐125(Ti) for RhB was 59.92 mg g^?1. MIL‐125(Ti) appears to be a promising material for RhB adsorption from aqueous solutions. Copyright © 2014 John Wiley & Sons, Ltd.     

Long‐Term Photostability in Terephthalate Metal–Organic Frameworks

Prolonged (weeks) UV/Vis irradiation under Ar of UiO‐66(Zr), UiO66 Zr‐NO₂, MIL101 Fe, MIL125 Ti‐NH₂, MIL101 Cr and MIL101 Cr(Pt) shows that these MOFs undergo photodecarboxylation of benzenedicarboxylate (BDC) linker in a significant percentage depending on the structure and composition of the material. Routine characterization techniques such as XRD, UV/Vis spectroscopy and TGA fail to detect changes in the material, although porosity and surface area change upon irradiation of powders. In contrast to BCD‐containing MOFs, zeolitic imidazolate ZIF‐8 does not evolve CO₂ or any other gas upon irradiation.     

Enhanced Electrocatalytic N2 Reduction via Partial Anion Substitution in Titanium Oxide–Carbon Composites

The electrochemical conversion of N₂ at ambient conditions using renewably generated electricity is an attractive approach for sustainable ammonia (NH₃) production. Considering the chemical inertness of N₂, rational design of efficient and stable catalysts is required. Therefore, in this work, it is demonstrated that a C‐doped TiO₂/C (C‐Ti_xO_y/C) material derived from the metal–organic framework (MOF) MIL‐125(Ti) can achieve a high Faradaic efficiency (FE) of 17.8 %, which even surpasses most of the established noble metal‐based catalysts. On the basis of the experimental results and theoretical calculations, the remarkable properties of the catalysts can be attributed to the doping of carbon atoms into oxygen vacancies (OVs) and the formation of Ti?C bonds in C‐Ti_xO_y. This binding motive is found to be energetically more favorable for N₂ activation compared to the non‐substituted OVs in TiO₂. This work elucidates that electrochemical N₂ reduction reaction (NRR) performance can be largely improved by creating catalytically active centers through rational substitution of anions into metal oxides.     

Preparation of BiVO4/MIL‐125(Ti) composite with enhanced visible‐light photocatalytic activity for dye degradation

Because of their desired features, including very specific surface areas and designable framework architecture together with their possibility to be functionalized, Metal Framework (MOF) is a promising platform for supporting varied materials in respect of catalytic applications in water treatment. In this work, a novel visible‐light‐responsive photocatalyst that comprised BiVO₄ together with MIL‐125(Ti), was synthesized by a two‐step hydrothermal approach. The characterization of as‐obtained samples as performed by X‐ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, Fourier transform infrared spectroscope, X‐ray photoelectron spectroscopy and ultraviolet‐visible diffuse reflection spectra. Rhodamine B was selected being a target for the evaluation of the photocatalytic function of as‐developed photocatalyst. The photocatalytic reaction parameters, for example, the content of BiVO₄ as well as initial concentration of Rhodamine B was researched. The composite photocatalyst possessing Bi:Ti molar ratio of 3:2 brought to light the fact that the greatest photocatalytic activity had the ability to degrade 92% of Rhodamine B in 180 min. In addition to that, the BiVO₄/MIL‐125(Ti) composite could keep its photocatalytic activity during the recycling test. The phenomenon of disintegration of the photo‐generated charges in the BiVO₄/MIL‐125(Ti) composite was brought to discussion as well.     

One‐pot self‐assembly and photoreduction synthesis of silver nanoparticle‐decorated reduced graphene oxide/MIL‐125(Ti) photocatalyst with improved visible light photocatalytic activity

In recent years, tremendous research efforts have been made towards developing metal–organic framework (MOF)‐based composites for photocatalytic applications. In this work, bipyramid‐like MIL‐125(Ti) frustum enwrapped with reduced graphene oxide (rGO) and dispersed silver nanoparticles (Ag NPs) was fabricated using an efficient one‐pot self‐assembly and photoreduction strategy. The as‐obtained materials were characterized using field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, nitrogen adsorption–desorption isotherms, and X‐ray photoelectron, ultraviolet–visible diffuse reflectance and photoluminescence spectroscopies. It is found that the as‐prepared Ag/rGO/MIL‐125(Ti) ternary hybrids have large surface area, microporous structure, enhanced visible light absorption and prolonged lifetime of charge carriers. Compared with pure MIL‐125(Ti) and its binary counterparts, the ternary composite exhibits more efficient photocatalytic performance for Rhodamine B (RhB) degradation from water under visible light irradiation. The photodegradation rate of RhB on Ag/rGO/MIL‐125(Ti) is 0.0644 min^?1, which is 1.62 times higher than that of the pure MIL‐125(Ti). The improved photocatalytic performance is ascribed to the indirect dye photosensitization, the Ag NP localized surface plasmon resonance, the Ti³⁺–Ti⁴⁺ intervalence electron transfer and the synergistic effect among MIL‐125(Ti), Ag NPs and rGO. Ag NPs serve as an efficient ‘electron reservoir’ and rGO as an electron transporter and collector. Therefore, this work provides a new pathway into the design of MOF‐based composites for application in environmental and energy fields. Copyright © 2016 John Wiley & Sons, Ltd.     

Yolk–shell microspheres assembled from Preyssler‐type NaP5W30O11014− polyoxometalate and MIL‐101(Cr) metal–organic framework: A new inorganic–organic nanohybrid for fast and selective removal of cationic organic dyes from aqueous media

Novel inorganic–organic yolk–shell microspheres based on Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate and MIL‐101(Cr) metal–organic framework (P₅W₃₀/MIL‐101(Cr)) were synthesized by reaction of K_12.5Na_1.5[NaP₅W₃₀O₁₁₀], Cr(NO₃)₃·9H₂O and terephthalic acid under hydrothermal conditions at 200°C for 24 h. The as‐prepared yolk–shell microspheres were fully characterized using various techniques. All analyses confirmed the incorporation of the Preyssler‐type NaP₅W₃₀O₁₁₀^14? polyoxometalate into the three‐dimensional porous MIL‐101(Cr) metal–organic framework. The results revealed that P₅W₃₀/MIL‐101(Cr) demonstrated rapid adsorption of cationic methylene blue (MB) and rhodamine B (RhB) with ultrahigh efficiency and capacity, as well as achieving rapid and highly selective adsorption of MB from MB/MO (MO = methyl orange), MB/RhB and MB/RhB/MO mixtures. The P₅W₃₀/MIL‐101(Cr) adsorbent not only exhibited a high adsorption capacity of 212 mg g^?1, but also could quickly remove 100% of MB from a dye solution of 50 mg l^?1 within 8 min. The effects of some key parameters such as adsorbent dosage, initial dye concentration and initial pH on dye adsorption were investigated in detail. The equilibrium adsorption data were better fitted by the Langmuir isotherm. The adsorption kinetics was well modelled using a pseudo‐second‐order model. Also, the inorganic–organic hybrid yolk–shell microspheres could be easily separated from the reaction system and reused up to four times without any change in structure or adsorption ability. The stability and robustness of the adsorbent were confirmed using various techniques.     

Fabrication of Heterostructured Fe2TiO5–TiO2 Nanocages with Enhanced Photoelectrochemical Performance for Solar Energy Conversion

Photocatalysts with well‐designed compositions and structures are desirable for achieving highly efficient solar‐to‐chemical energy conversion. Heterostructured semiconductor photocatalysts with advanced hollow structures possess beneficial features for promoting the activity towards photocatalytic reactions. Here we develop a facile synthetic strategy for the fabrication of Fe₂TiO₅–TiO₂ nanocages (NCs) as anode materials in photoelectrochemical (PEC) water splitting cells. A hydrothermal reaction is performed to transform MIL‐125(Ti) nanodisks (NDs) to Ti–Fe–O NCs, which are further converted to Fe₂TiO₅–TiO₂ NCs through a post annealing process. Owing to the compositional and structural advantages, the heterostructured Fe₂TiO₅–TiO₂ NCs show enhanced performance for PEC water oxidation compared with TiO₂ NDs, Fe₂TiO₅ nanoparticles (NPs) and Fe₂TiO₅–TiO₂ NPs.     

Mechanochemical Immobilisation of Metathesis Catalysts in a Metal–Organic Framework

A simple, one‐step mechanochemical procedure for immobilisation of homogeneous metathesis catalysts in metal–organic frameworks was developed. Grinding MIL‐101‐NH₂(Al) with a Hoveyda–Grubbs second‐generation catalyst resulted in a heterogeneous catalyst that is active for metathesis and one of the most stable immobilised metathesis catalysts. During the mechanochemical immobilisation the MIL‐101‐NH₂(Al) structure was partially converted to MIL‐53‐NH₂(Al). The Hoveyda–Grubbs catalyst entrapped in MIL‐101‐NH₂(Al) is responsible for the observed catalytic activity. The developed synthetic procedure was also successful for the immobilisation of a Zhan catalyst.     

Two‐Phase System Utilizing Hydrophobic Metal–Organic Frameworks (MOFs) for Photocatalytic Synthesis of Hydrogen Peroxide

Much effort has been devoted to photocatalytic production of hydrogen peroxide (H₂O₂) as an alternative to fossil fuels. From an economic point of view, reductive synthesis of H₂O₂ from O₂ coupled with the oxidative synthesis of value‐added products is particularly interesting. We herein report application of MIL‐125‐NH₂, a photoactive metal–organic framework (MOF), to a benzylalcohol/water two‐phase system that realized photocatalytic production and spontaneous separation of H₂O₂ and benzaldehyde. Hydrophobization of the MOF enabled its separation from the aqueous phase. This resulted in enhanced photocatalytic efficiency and enabled application of various aqueous solutions including extremely low pH solution which is favorable for H₂O₂ production but fatal to MOF structure. In addition, a highly concentrated H₂O₂ solution was obtained by simply reducing the volume of the aqueous phase.     

Ce2Ti2SiO9 – das erste Titanat‐Silicat mit Cer – Präparation,Charakterisierung und Struktur

Ce₂Ti₂SiO₉ – the First Titanate‐Silicate with Cerium – Preparation, Characterization, and Structure Ce₂Ti₂SiO₉ was synthesized by chemical vapour transport in a temperature gradient (1050 °C → 900 °C) using Ce₂Ti₂O₇ as precursor and ammoniumchloride as transport agent. SiO₂ was provided from the wall of the used silica tubes. The chemical composition of the crystals was determined by EDX and EELS analysis. The structure of Ce₂Ti₂SiO₉ was determined and refined to R1 = 0.025, _wR2 = 0.067, respectively. The monoclinic phase crystallizes in the space group C2/m (No. 12) with a = 16.907(3) Å, b = 5.7078(8) Å, c = 7.574(2) Å, β = 111.38(2)° and Z = 4. Ti is octahedral, Si is tetrahedral surrounded by oxygen. Ce(1) is coordinated by eight, Ce(2) by ten oxygen atoms. There are edge connected chains of Ti(1)–O‐octahedra parallel [010] which are connected along [001] with each other by Ti(2)–O‐octahedra‐pairs and Si–O‐tetrahedra.     

Bifunctional Electrocatalysts for Overall Water Splitting from an Iron/Nickel‐Based Bimetallic Metal–Organic Framework/Dicyandiamide Composite

Pyrolysis of a bimetallic metal–organic framework (MIL‐88‐Fe/Ni)‐dicyandiamide composite yield a Fe and Ni containing carbonaceous material, which is an efficient bifunctional electrocatalyst for overall water splitting. FeNi₃ and NiFe₂O₄ are found as metallic and metal oxide compounds closely embedded in an N‐doped carbon–carbon nanotube matrix. This hybrid catalyst (Fe‐Ni@NC‐CNTs) significantly promotes the charge transfer efficiency and restrains the corrosion of the metallic catalysts, which is shown in a high OER and HER activity with an overpotential of 274 and 202 mV, respectively at 10 mA cm^?2 in alkaline solution. When this bifunctional catalyst was further used for H₂ and O₂ production in an electrochemical water‐splitting unit, it can operate in ambient conditions with a competitive gas production rate of 1.15 and 0.57 μL s^?1 for hydrogen and oxygen, respectively, showing its potential for practical applications.     

Magnetic iron(III)‐based framework composites for the magnetic solid‐phase extraction of fungicides from environmental water samples

We adopted a facile hydrofluoric acid‐free hydro‐/solvothermal method for the preparation of four magnetic iron(III)‐based framework composites (MIL‐101@Fe₃O₄‐COOH, MIL‐101‐NH₂@Fe₃O₄‐COOH, MIL‐53@Fe₃O₄‐COOH, and MIL‐53‐NH₂@Fe₃O₄‐COOH). The obtained four magnetic iron(III)‐based framework composites were applied to magnetic separation and enrichment of the fungicides (prochloraz, myclobutanil, tebuconazole, and iprodione) from environmental samples before high‐performance liquid chromatographic analysis. MIL‐101‐NH₂@Fe₃O₄‐COOH showed more remarkable pre‐concentration ability for the fungicides as compared to the other three magnetic iron(III)‐based framework composites. The extraction parameters affecting enrichment efficiency including extraction time, sample pH, elution time, and the desorption solvent were investigated and optimized. Under the optimized conditions, the standard curve of correlation coefficients were all above 0.991, the limits of detection were 0.04–0.4 μg/L, and the relative standard deviations were below 10.2%. The recoveries of two real water samples ranged from 71.1–99.1% at the low spiking level (30 μg/L). Therefore, the MIL‐101‐NH₂@Fe₃O₄‐COOH composites are attractive for the rapid and efficient extraction of fungicides from environmental water samples.     

High Impact of Uranyl Ions on Carrying–Releasing Oxygen Capability of Hemoglobin‐Based Blood Substitutes

The effect of radioactive UO₂²⁺ on the oxygen‐transporting capability of hemoglobin‐based oxygen carriers has been investigated in vitro. The hemoglobin (Hb) microspheres fabricated by the porous template covalent layer‐by‐layer (LbL) assembly were utilized as artificial oxygen carriers and blood substitutes. Magnetic nanoparticles of iron oxide (Fe₃O₄) were loaded in porous CaCO₃ particles for magnetically assisted chemical separation (MACS). Through the adsorption spectrum of magnetic Hb microspheres after adsorbing UO₂²⁺, it was found that UO₂²⁺ was highly loaded in the magnetic Hb microspheres, and it shows that the presence of UO₂²⁺ in vivo destroys the structure and oxygen‐transporting capability of Hb microspheres. In view of the high adsorption capacity of UO₂²⁺, the as‐assembled magnetic Hb microspheres can be considered as a novel, highly effective adsorbent for removing metal toxins from radiation‐contaminated bodies, or from nuclear‐power reactor effluent before discharge into the environment.     

Nanoscale Trimetallic Metal–Organic Frameworks Enable Efficient Oxygen Evolution Electrocatalysis

Metal–organic frameworks (MOFs) are a class of promising materials for diverse heterogeneous catalysis, but they are usually not directly employed for oxygen evolution electrocatalysis. Most reports focus on using MOFs as templates to in situ create efficient electrocatalysts through annealing. Herein, we prepared a series of Fe/Ni‐based trimetallic MOFs (Fe/Ni/Co(Mn)‐MIL‐53 accordingly to the Material of Institute Lavoisier) by solvothermal synthesis, which can be directly adopted as highly efficient electrocatalysts. The Fe/Ni/Co(Mn)‐MIL‐53 shows a volcano‐type oxygen evolution reaction (OER) activity as a function of compositions. The optimized Fe/Ni_2.4/Co_0.4‐MIL‐53 can reach a current density of 20 mA cm^?2 at low overpotential of 236 mV with a small Tafel slope of 52.2 mV dec^?1. In addition, the OER performance of these MOFs can be further enhanced by directly being grown on nickel foam (NF).     

Synthesis,Water Adsorption,and Proton Conductivity of Solid‐Solution‐Type Metal–Organic Frameworks Al(OH)(bdc‐OH)x(bdc‐NH2)1−x

Mixed‐ligand metal–organic frameworks Al(bdc‐OH)_x(bdc‐NH₂)_1?x (H₂bdc‐NH₂=aminoterepthalic acid, H₂bdc‐OH=hydroxyterephthalic acid) were synthesized and their water adsorption behavior and proton conductivity were investigated. All obtained compounds were isostructural to MIL‐53 (MIL=Materials of Institut Lavoisier) according to XRD measurements under ambient humidity conditions, and were also found to be single phase across the whole mixing ratio from the XRD measurements under humidified conditions. This result clearly shows that all compounds are a solid‐solution‐type mixture of ligands. MIL‐53‐NH₂ adsorbs one water molecule per formula with humidification whereas MIL‐53‐OH adsorbs five water molecules. The mixing ratio of the ligands in Al(OH)(bdc‐OH)_x(bdc‐NH₂)_1?x affected the gate‐opening pressure for water adsorption and total water uptake. Proton conductivity of these compounds largely depends on the adsorbed amount of water, which indicates that the proton conductivity of these compounds depends strongly on the hydrogen‐bond network of the conducting media.     

Comparisons of glyphosate adsorption properties of different functional Cr‐based metal–organic frameworks

A Cr‐based metal–organic framework, namely, MIL‐101(Cr), was modified with amino (NH₂–) and urea (UR₂–) groups, and the materials were evaluated as adsorbents for glyphosate, and a comparison with commercial activated carbon was also discussed. The effects of the adsorption factors, such as adsorbent concentration, adsorption time, pH and ionic strength were mainly investigated. The results showed that a pseudo‐second‐order rate equation described the adsorption kinetics mechanisms well, while the Langmuir model and the Freundlich model fitted different adsorption isotherms, respectively. Among the adsorbents we studied, NH₂‐MIL‐101(Cr) showed the maximum adsorbing capacity, which is 64.25 mg/g when pH = 3.0, while UR₂‐MIL‐101(Cr) did not reach the best adsorption performance due to the steric hindrance. The work opens up a new way for the modification of metal–organic frameworks for adsorption process.     

Enhancing photocatalytic activity of titanium dioxide through incorporation of MIL‐53(Fe) toward degradation of organic dye

Photocatalytic activity of titanium(IV) oxide (TiO₂) can be enhanced through modification of its surface‐active sites. Here, iron(III) carboxylate [MIL‐53[Fe]]‐incorporated TiO₂ (as MIL‐53(Fe)/TiO₂) was prepared using a hydrothermal method. This material was then calcined at 500°C to obtain a MIL‐53(Fe)‐derived γ‐Fe₂O₃/TiO₂ photocatalyst. A photocatalytic study of MIL‐53(Fe)/TiO₂ and MIL‐53(Fe)‐derived γ‐Fe₂O₃/TiO₂ toward cationic methylene blue (MB) and anionic methyl orange (MO) showed that MIL‐53(Fe)/TiO₂ (0.25 wt%) and MIL‐53(Fe)‐derived γ‐Fe₂O₃/TiO₂ (0.75 wt%) resulted the best degree of dye degradation. The MIL‐53(Fe)‐derived γ‐Fe₂O₃/TiO₂ (0.75 wt%) composite for instance is capable of degrading almost 100% of 20‐ppm MB and MO, respectively, within 6 hr. Photocatalytic degradation of MB and MO was well fitted to the Langmuir‐Hinshelwood pseudo‐first order kinetics model, which indicates physisorption as the key partway that facilitates dye decomposition on the surface of a photocatalyst under UV‐A irradiation. This study provides new insights into the exploration of MILs/TiO₂ materials for the environmental remediation and pollution control.