Metal-Organic Frameworks as Photocatalysts for Solar-Driven Overall Water Splitting.

Metal-organic frameworks (MOFs) have been frequently used as photocatalysts for the hydrogen evolution reaction (HER) using sacrificial agents with UV-vis or visible light irradiation. The aim of the present review is to summarize the use of MOFs as solar-driven photocatalysts targeting to overcome the current efficiency limitations in overall water splitting (OWS). Initially, the fundamentals of the photocatalytic OWS under solar irradiation are presented. Then, the different strategies that can be implemented on MOFs to adapt them for solar photocatalysis for OWS are discussed in detail. Later, the most active MOFs reported until now for the solar-driven HER and/or oxygen evolution reaction (OER) are critically commented. These studies are taken as precedents for the discussion of the existing studies on the use of MOFs as photocatalysts for the OWS under visible or sunlight irradiation. The requirements to be met to use MOFs at large scale for the solar-driven OWS are also discussed. The last section of this review provides a summary of the current state of the field and comments on future prospects that could bring MOFs closer to commercial application.

Selective Gas-Phase Hydrogenation of CO2 to Methanol Catalysed by Metal-Organic Frameworks.

Large scale production of green CH3 OH obtained from CO2 and green H2 is a highly wanted process due to the role of CH3 OH as H2 /energy carrier and for producing chemicals. Starting with a short summary of the advantages of metal-organic frameworks (MOFs) as catalysts in liquid-phase reactions, the present article highlights the opportunities that MOFs may offer also for some gas-phase reactions, particularly for the selective CO2 hydrogenation to CH3 OH. It is commented that there is a temperature compatibility window that combines the thermal stability of some MOFs with the temperature required in the CO2 hydrogenation to CH3 OH that frequently ranges from 250 to 300 °C. The existing literature in this area is briefly organized according to the role of MOF as providing the active sites or as support of active metal nanoparticles (NPs). Emphasis is made to show how the flexibility in design and synthesis of MOFs can be used to enhance the catalytic activity by adjusting the composition of the nodes and the structure of the linkers. The influence of structural defects and material crystallinity, as well as the role that should play theoretical calculations in models have also been highlighted.

Translocation and Confinement of Tetraamines in Adaptable Microporous Cavities.

Metal-Organic Frameworks can be grafted with amines by coordination to metal vacancies to create amine-appended solid adsorbents, which are being considered as an alternative to using aqueous amine solutions for CO2 capture. In this study, we propose an alternative mechanism that does not rely on the use of neutral metal vacancies as binding sites but is enabled by the structural adaptability of heterobimetallic Ti2Ca2 clusters. The combination of hard (Ti4+) and soft (Ca2+) metal centers in the inorganic nodes of the framework enables MUV-10 to adapt its pore windows to the presence of triethylenetetramine molecules. This dynamic cluster response facilitates the translocation and binding of tetraamine inside the microporous cavities to enable the formation of bis-coordinate adducts that are stable in water. The extension of this grafting concept from MUV-10 to larger cavities not restrictive to CO2 diffusion will complement other strategies available for the design of molecular sorbents for decarbonization applications.

Metal Node Control of Brønsted Acidity in Heterobimetallic Titanium-Organic Frameworks.

Compared to indirect framework modification, synthetic control of cluster composition can be used to gain direct access to catalytic activities exclusive of specific metal combinations. We demonstrate this concept by testing the aminolysis of epoxides with a family of isostructural mesoporous frameworks featuring five combinations of homometallic and heterobimetallic metal-oxo trimers (Fe3, Ti3, TiFe2, TiCo2, and TiNi2). Only TiFe2 nodes display activities comparable to benchmark catalysts based on grafting of strong acids, which here originate from the combination of Lewis Ti4+ and Brønsted Fe3+-OH acid sites. The applicability of MUV-101(Fe) to the synthesis of ß-amino alcohols is demonstrated with a scope that also includes the gram scale synthesis of propranolol, a natural ß-blocker listed as an essential medicine by the World Health Organization, with excellent yield and selectivity.

Porphyrin-Based MOF Thin Film on Transparent Conducting Oxide: Investigation of Growth, Porosity and Photoelectrochemical Properties.

Synthesizing metal-organic frameworks (MOFs) composites with a controlled morphology is an important requirement to access materials of desired patterning and composition. Since the last decade, MOF growth from sacrificial metal oxide layer is increasingly developed as it represents an efficient pathway to functionalize a large number of substrates. In this study, porphyrin-based Al-PMOF thin films were grown on conductive transparent oxide substrates from sacrificial layers of ALD-deposited alumina oxide. The control of the solvent composition and the number of atomic layer deposition (ALD) cycles allow us to tune the crystallinity, morphology and thickness of the produced thin films. Photophysical studies evidence that Al-PMOF thin films present light absorption and emission properties governed by the porphyrinic linker, without any quenching upon increasing the film thickness. Al-PMOF thin films obtained through this methodology present a remarkably high optical quality both in terms of transparency and coverage. The porosity of the samples is demonstrated by ellipsometry and used for Zn(II) insertion inside the MOF thin film. The multifunctional transparent, porous and luminescent thin film grown on fluorine-doped tin oxide (FTO) is used as an electrode capable of photoinduced charge separation upon simulated sunlight irradiation.

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.

Bifunctional metal-organic frameworks for the hydrogenation of nitrophenol using methanol as the hydrogen source.

This work reports the reduction of 4-nitrophenol to 4-aminophenol using UiO-66(Zr) as a bifunctional photocatalyst and hydrogenation catalyst using methanol as the hydrogen source. In particular, a series of UiO-66(Zr)-X (X: NH2, NO2 and H) and MIL-125(Ti)-NH2 catalysts have been screened as bifunctional catalysts for this process. UiO-66(Zr)-NH2 was found to be the most active material to promote light-assisted nitro hydrogenation under both UV-Vis and simulated sunlight irradiation. The tandem reaction occurs via hydrogen generation from a water/methanol mixture in the first step and, then, reduction of 4-nitrophenol to 4-aminophenol. UiO-66(Zr)-NH2 acts as a truly heterogeneous catalyst and can be reused several times without significant loss of activity, maintaining its crystallinity. This work shows the possibility of using MOFs as solar-driven bifunctional catalysts to promote the hydrogenation of organic compounds using methanol as the hydrogen source.

Selective Implantation of Diamines for Cooperative Catalysis in Isoreticular Heterometallic Titanium-Organic Frameworks.

We introduce the first example of isoreticular titanium-organic frameworks, MUV-10 and MUV-12, to show how the different affinity of hard Ti(IV) and soft Ca(II) metal sites can be used to direct selective grafting of amines. This enables the combination of Lewis acid titanium centers and available -NH2 sites in two sizeable pores for cooperative cycloaddition of CO2 to epoxides at room temperature and atmospheric pressure. The selective grafting of molecules to heterometallic clusters adds up to the pool of methodologies available for controlling the positioning and distribution of chemical functions in precise positions of the framework required for definitive control of pore chemistry.

Plasma-Induced Defects Enhance the Visible-Light Photocatalytic Activity of MIL-125(Ti)-NH2 for Overall Water Splitting.

Defect engineering in metal-organic frameworks is commonly performed by using thermal or chemical treatments. Herein we report that oxygen plasma treatment generates structural defects on MIL-125(Ti)-NH2 , leading to an increase in its photocatalytic activity. Characterization data indicate that plasma-treated materials retain most of their initial crystallinity, while exhibiting somewhat lower surface area and pore volume. XPS and FT-IR spectroscopy reveal that oxygen plasma induces MIL-125(Ti)-NH2 partial terephthalate decarboxylation and an increase in the Ti-OH population. Thermogravimetric analyses confirm the generation of structural defects by oxygen plasma and allowed an estimation of the resulting experimental formula of the treated MIL-125(Ti)-NH2 solids. SEM analyses show that oxygen plasma treatment of MIL-125(Ti)-NH2 gradually decreases its particle size. Importantly, diffuse reflectance UV/Vis spectroscopy and valence band measurements demonstrate that oxygen plasma treatment alters the MIL-125(Ti)-NH2 band gap and, more significantly, the alignment of highest occupied and lowest unoccupied crystal orbitals. An optimal oxygen plasma treatment to achieve the highest efficiency in water splitting with or without methanol as sacrificial electron donor under UV/Vis or simulated sunlight was determined. The optimized plasma-treated MIL-125(Ti)-NH2 photocatalyst acts as a truly heterogeneous photocatalyst and retains most of its initial photoactivity and crystallinity upon reuse.

A Semiconducting Bi2O2(C4O4) Coordination Polymer Showing a Photoelectric Response.

Inorganic semiconductors are extensively considered to be among the most promising materials to convert solar light into electricity or chemical energy owing to their efficiency in the separation of photoinduced electron/hole. Bismuth oxides, and, in particular, those built up of [Bi2O2]2+ layers, show an efficient charge separation and, thus, high photocatalytic activities. To explore a possible synergetic effect of bismuth metallic nodes combined with the electron-rich linker squarate, Bi2O2(C4O4) or IEF-3 (an IMDEA Energy framework) was hydrothermally prepared and adequately characterized. As determined from the X-ray structure, [Bi2O2]2+ layers are interconnected by squarate ligands, having a pronounced effect of the 6s2 lone pair on the bismuth local environment. IEF-3 shows high thermal and chemical robustness at industrially relevant model aggressive media. A large panel of physicochemical methods were applied to recognize IEF-3 as an UV-absorbing n-type semiconductor, showing a photocurrent response comparable to that of α-Bi2O3, offering further possibilities for tuning its electrochemical properties by modifying the ligand. In this way, the well-known compositional and structural versatility of coordination polymers may be applied in the future to fine-tune metal-organic semiconductor systems.

Tuning the Microenvironment of Gold Nanoparticles Encapsulated within MIL-101(Cr) for the Selective Oxidation of Alcohols with O2 : Influence of the Amino Terephthalate Linker.

This manuscript reports a comparative study of the catalytic performance of gold nanoparticles (NPs) encapsulated within MIL-101(Cr) with or without amino groups in the terephthalate linker. The purpose is to show how the amino groups can influence the microenvironment and catalytic stability of incorporated gold nanoparticles. The first influence of the presence of this substituent is the smaller particle size of Au NPs hosted in MIL-101(Cr)-NH2 (2.45±0.19 nm) compared with the parent MIL-101(Cr)-H (3.02±0.39 nm). Both materials are highly active to promote the aerobic alcohol oxidation and exhibit a wide substrate scope. Although both catalysts can achieve turnover numbers as high as 106 for the solvent-free aerobic oxidation of benzyl alcohol, Au@MIL-101(Cr)-NH2 exhibits higher turnover frequency values (12 000 h-1 ) than Au@MIL-101(Cr)-H (6800 h-1 ). Au@MIL-101(Cr)-NH2 also exhibits higher catalytic stability, being recyclable for 20 times with coincident temporal conversion profiles, in comparison with some decay observed in the parent Au@MIL-101(Cr)-H. Characterization by transmission electron microscopy of the 20-times used samples shows a very minor particle size increase in the case of Au@MIL-101(Cr)-NH2 (2.97±0.27 nm) in comparison with the Au@MIL-101(Cr)-H analog (5.32±0.72 nm). The data presented show the potential of better control of the microenvironment to improve the performance of encapsulated Au nanoparticles.

A translational approach to assess the metabolomic impact of stabilized gold nanoparticles by NMR spectroscopy.

Gold nanoparticles have high potential in the biomedical area, especially in disease diagnosis and treatment. The application of these nanoparticles requires the presence of stabilizers to avoid their agglomeration. Nowadays, there is a lack of reliable methods for characterising the effect of stabilised nanoparticles on biological systems. To this end, in this study, we apply an experimental approach based on nuclear magnetic resonance spectroscopy to study the effect of gold nanoparticles, stabilised with cerium oxide or chitosan, on a human cancer cell model. The results showed that both systems have a significant effect, even at non-toxic levels, on the cellular antioxidant system. However, although particles functionalised with chitosan exerted a strong effect on the aerobic respiration, nanoparticles stabilised with cerium oxide had a higher impact on the mechanisms associated with anaerobic energy production. Therefore, even though both systems contained similar gold nanoparticles, the presence of different stabilizers strongly influenced their mode of action and potential applications in biomedicine.

Encapsulation of Metal Nanoparticles within Metal-Organic Frameworks for the Reduction of Nitro Compounds.

Nitro group reduction is a reaction of a considerable importance for the preparation of bulk chemicals and in organic synthesis. There are reports in the literature showing that incorporation of metal nanoparticles (MNPs) inside metal-organic frameworks (MOFs) is a suitable strategy to develop catalysts for these reactions. Some of the examples reported in the literature have shown activity data confirming the superior performance of MNPs inside MOFs. In the present review, the existing literature reports have been grouped depending on whether these MNPs correspond to a single metal or they are alloys. The final section of this review summarizes the state of the art and forecasts future developments in the field.

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.

Active sites on graphene-based materials as metal-free catalysts.

Graphenes and related materials have attracted growing interest as metal-free catalysts. The present review is focused on describing the active sites that have been proposed to be responsible for the catalytic activity observed for such systems. It will be shown that diverse defects and chemical functionalities on the graphene layers can catalyze reactions, including oxygenated functional groups, carbon vacancies and holes, edge effects, and the presence of dopant elements. Besides discrete active sites, the catalytic activity arising from the collective properties of graphenes as materials by adsorbing substrates and reagents and activating them by charge transfer is also commented. The review has an introductory general section summarizing the general methodologies that have been used to support the proposed structure of the active sites, including theoretical calculations, comparison of the catalytic activity of graphene samples with different compositions, the use of organic molecules as models of the active centers, and selective masking of functional groups. The review is concluded with our view on future developments in the field.

Covalently Modified Graphenes in Catalysis, Electrocatalysis and Photoresponsive Materials.

The ideal graphene is a one-atom thick single layer of carbon atoms having sp2 hybridation in hexagonal arrangement. Due to their large surface area and good dispersability in common solvents, graphenes are suitable platforms to anchor covalently units. The appended unit can introduce additional functionality to graphene. Although the field of covalently modified graphene is still starting compared to the development of other carbon nanoforms, there is already many examples describing the use of modified graphenes as recoverable photo-, electrocatalysts as well as in non-linear optics and to improve mechanical resistance and solubility of graphenes. In this Review, the state of the art of covalently modified graphenes for these applications is reviewed. After some general sections describing properties and characterization techniques of graphenes relevant to their use as supports and those general reactions and starting substrates to obtain the modified graphene conjugates, the main body of the review describes the preparation and properties of covalently modified graphene depending on their use as catalyst, photocatalyst, photoresponsive material, non-linear optics, electrocatalyst and other uses. The last section of the review summarizes the main achievements of the field and what should be according to our view the future developments.

Chitosan-templated synthesis of few-layers boron nitride and its unforeseen activity as a Fenton catalyst.

A novel procedure for the preparation of few-layers boron nitride (BN), either as films or as suspended BN platelets, is presented, based on the pyrolysis of chitosan, which serves both as a matrix to embed ammonium borate and as a template for BN synthesis. The resulting BN samples are characterized by XRD, Raman and X-ray photoelectron spectroscopy, and by TEM and AFM imaging. The samples exhibit deep UV emission, which is characteristic of high quality BN. This template synthesis and the easy exfoliation of BN platelets facilitate the use of BN as an extremely high-efficiency Fenton catalyst for the generation of highly aggressive hydroxyl radicals in water.

Graphenes as Efficient Metal-Free Fenton Catalysts.

Reduced graphene oxide exhibits high activity as Fenton catalyst with HO(.) radical generation efficiency over 82 % and turnover numbers of 4540 and 15023 for phenol degradation and H2 O2 consumption, respectively. These values compare favorably with those achieved with transition metals, showing the potential of carbocatalysts for the Fenton reaction.

Hydrogel composites based on chitosan and CuAuTiO2 photocatalysts for hydrogen production under simulated sunlight irradiation.

This study explored the photocatalytic hydrogen evolution reaction (HER) using novel biohydrogel composites comprising chitosan, and a photocatalyst consisting in TiO2 P25 decorated with Au and/or Cu mono- and bimetallic nanoparticles (NPs) to boost its optical and catalytic properties. Low loads of Cu and Au (1 mol%) were incorporated onto TiO2 via a green photodeposition methodology. Characterization techniques confirmed the incorporation of decoration metals as well as improvements in the light absorption properties in the visible light interval (λ > 390 nm) and electron transfer capability of the semiconductors. Thereafter, Au and/or Cu NP-supported TiO2 were incorporated into chitosan-based physically crosslinked hydrogels revealing significant interactions between chitosan functional groups (hydroxyls, amines and amides) with the NPs to ensure its encapsulation. These materials were evaluated as photocatalysts for the HER using water and methanol mixtures under simulated sunlight and visible light irradiation. Sample CuAuTiO2/ChTPP exhibited a maximum hydrogen generation of 1790 µmol g-1 h-1 under simulated sunlight irradiation, almost 12-folds higher compared with TiO2/ChTPP. Also, the nanocomposites revealed a similar tendency under visible light with a maximum hydrogen production of 590 µmol g-1 h-1. These results agree with the efficiency of photoinduced charge separation revealed by transient photocurrent and EIS.

Valorization of Field-Spent Granular Activated Carbon as Heterogeneous Ozonation Catalyst for Water Treatment.

Developing sustainable cost-effective strategies for valorization of field-spent granular activated carbon (s-GAC) from industrial water treatment has gained much interest. Here, we report a cost-effective strategy for the regeneration of s-GAC as an adsorbent in a large-scale drinking water treatment plant and used as an efficient and durable ozonation catalyst in water. To achieve this, a series of samples is prepared by subjecting s-GAC to thermally controlled combustion treatments with and without pyrolysis. The catalytic performance of the optimized sample is evaluated for oxalic acid degradation as the model pollutant under batch (>15 h) and continuous flow operations (>200 h). The partially deactivated catalyst upon reuse is restored by thermal treatment. Electron paramagnetic resonance and selective quenching experiments show the formation of singlet oxygen (1O2) during catalytic ozonation. The GAC-ozonation catalyst is efficient to minimize the formation of chlorinated disinfection by-products like trihalomethanes and haloacetic acids in an urban wastewater effluent.