Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long

Carbon Dioxide Capture in Metal–Organic Frameworks

Fujishima and Honda (1972) demonstrated the potential of titanium dioxide (TiO2) semiconductor materials to split water into hydrogen and oxygen in a photo-electrochemical cell. Their work triggered the development of semiconductor photocatalysis for a wide range of environmental and energy applications. One of the most significant scientific and commercial advances to date has been the development of visible light active (VLA) TiO2 photocatalytic materials. In this review, a background on TiO2 structure, properties and electronic properties in photocatalysis is presented. The development of different strategies to modify TiO2 for the utilization of visible light, including non metal and/or metal doping, dye sensitization and coupling semiconductors are discussed. Emphasis is given to the origin of visible light absorption and the reactive oxygen species generated, deduced by physicochemical and photoelectrochemical methods. Various applications of VLA TiO2, in terms of environmental remediation and in particular water treatment, disinfection and air purification, are illustrated. Comprehensive studies on the photocatalytic degradation of contaminants of emerging concern, including endocrine disrupting compounds, pharmaceuticals, pesticides, cyanotoxins and volatile organic compounds, with VLA TiO2 are discussed and compared to conventional UV-activated TiO2 nanomaterials. Recent advances in bacterial disinfection using VLA TiO2 are also reviewed. Issues concerning test protocols for real visible light activity and photocatalytic efficiencies with different light sources have been highlighted.

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A review on the visible light active titanium dioxide photocatalysts for environmental applications

Semiconductor photocatalysis has received much attention as a potential solution to the worldwide energy shortage and for counteracting environmental degradation. This article reviews state-of-the-art research activities in the field, focusing on the scientific and technological possibilities offered by photocatalytic materials. We begin with a survey of efforts to explore suitable materials and to optimize their energy band configurations for specific applications. We then examine the design and fabrication of advanced photocatalytic materials in the framework of nanotechnology. Many of the most recent advances in photocatalysis have been realized by selective control of the morphology of nanomaterials or by utilizing the collective properties of nano-assembly systems. Finally, we discuss the current theoretical understanding of key aspects of photocatalytic materials. This review also highlights crucial issues that should be addressed in future research activities.

Nano‐photocatalytic Materials: Possibilities and Challenges

2.2. MOFs with Metal Active Sites 4614 2.2.1. Early Studies 4614 2.2.2. Hydrogenation Reactions 4618 2.2.3. Oxidation of Organic Substrates 4620 2.2.4. CO Oxidation to CO2 4626 2.2.5. Phototocatalysis by MOFs 4627 2.2.6. Carbonyl Cyanosilylation 4630 2.2.7. Hydrodesulfurization 4631 2.2.8. Other Reactions 4632 2.3. MOFs with Reactive Functional Groups 4634 2.4. MOFs as Host Matrices or Nanometric Reaction Cavities 4636

Engineering Metal Organic Frameworks for Heterogeneous Catalysis

Since the early development of this technology in the 1970s, TiO2 constitutes the archetypical photocatalyst due to its relatively high efficiency, low cost and availability. However, during the last decade a considerable number of new photocatalytic materials, either semiconductor or not, have been proposed as potential substitutes of TiO2, particularly in the case of solar applications, for which this standard photocatalyst is not very suitable because of its wide band gap. Semiconductors based on cations with d0 configuration such Ta5+ or Nb5+, as well as oxides or nitrides of d10 elements such as Bi3+, In3+ or Ga3+ are among the most successful novel photocatalysts, but non-semiconductor solids like cation-interchanged zeolites also produce interesting results. In addition, some classical semiconductors like ZnO or CdS, initially discarded as a consequence of their poor stability under irradiation, have been reconsidered as feasible photocatalysts for particular applications. This growing body of data requires new analysis of the challenges and opportunities facing photocatalysis in order to assess which of the photoactive materials are best for each particular application. In this review, we summarize, with an historical perspective, the main achievements obtained with photocatalyst alternatives to TiO2 in the three main niches for this technology: water splitting for hydrogen production, decontamination and disinfection processes, and organic synthesis.

Development of alternative photocatalysts to TiO2: Challenges and opportunities

Amino-based metal-organic frameworks as stable, highly active basic catalysts

Photo frame(work): The first spectroscopic evidence of metal-organic frameworks (MOFs) acting as photocatalysts has been obtained. Isoreticular MOFs act as efficient photocatalysts in the photooxidation of propylene. The band gap energy can be tuned by changing the organic linker. Among the MOFs tested, the 2,6-naphthalenedicarboxylic acid based IRMOF was the most active, showing a higher activity than ZnO.

María D. Hernández-Alonso

Papers

Development of alternative photocatalysts to TiO2: Challenges and opportunities

Amino-based metal-organic frameworks as stable, highly active basic catalysts

Isoreticular MOFs as Efficient Photocatalysts with Tunable Band Gap: An Operando FTIR Study of the Photoinduced Oxidation of Propylene

Visible light-activated nanosized doped-TiO2 photocatalysts

Nanosize Ti–W Mixed Oxides: Effect of Doping Level in the Photocatalytic Degradation of Toluene Using Sunlight-Type Excitation