Maxim A. Nasalevich

Metal–organic frameworks as heterogeneous photocatalysts: advantages and challenges

The use of metal organic frameworks (MOFs) as heterogeneous photocatalysts is critically reviewed. First we revisit the general assumption of MOFs behaving truly as semiconductors, demonstrating that such semiconducting behaviour only occurs in a very limited subset of materials. Further, the main approaches for efficient light harvesting and active site engineering in MOF-based photocatalysts are discussed. Finally, the main advantages of MOFs as photocatalysts and the challenges that need to be addressed in order to improve catalytic performance are evaluated.

Co@NH2-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H2 production

We present a synthetic strategy for the efficient encapsulation of a derivative of a well-defined cobaloxime proton reduction catalyst within a photoresponsive metal–organic framework (NH2-MIL-125(Ti)). The resulting hybrid system Co@MOF is demonstrated to be a robust heterogeneous composite material. Furthermore, Co@MOF is an efficient and fully recyclable noble metal-free catalyst system for light-driven hydrogen evolution from water under visible light illumination.

Metal organic framework-mediated synthesis of highly active and stable Fischer-Tropsch catalysts

Depletion of crude oil resources and environmental concerns have driven a worldwide research on alternative processes for the production of commodity chemicals. Fischer-Tropsch synthesis is a process for flexible production of key chemicals from synthesis gas originating from non-petroleum-based sources. Although the use of iron-based catalysts would be preferred over the widely used cobalt, manufacturing methods that prevent their fast deactivation because of sintering, carbon deposition and phase changes have proven challenging. Here we present a strategy to produce highly dispersed iron carbides embedded in a matrix of porous carbon. Very high iron loadings (>40 wt %) are achieved while maintaining an optimal dispersion of the active iron carbide phase when a metal organic framework is used as catalyst precursor. The unique iron spatial confinement and the absence of large iron particles in the obtained solids minimize catalyst deactivation, resulting in high active and stable operation.

Insights into the Catalytic Performance of Mesoporous H-ZSM-5-Supported Cobalt in Fischer–Tropsch Synthesis

Mesoporous H‐ZSM‐5 (mesoH‐ZSM‐5) was used as a carrier for a series of bifunctional Co‐based catalysts for Fischer–Tropsch synthesis with ZrO2 and/or Ru added as promoters. The reducibility of the catalysts was studied in detail by using temperature‐programmed reduction and X‐ray absorption spectroscopy. A comparison of the catalytic performance of Co/mesoH‐ZSM‐5 and Co/SiO2 (a conventional catalyst), after 140 h on stream, reveals that the former is two times more active and three times more selective to the C5–C11 fraction with a large content of unsaturated hydrocarbons, which is next to α‐olefins. The acid‐catalyzed conversion of n‐hexane and 1‐hexene, as model reactions, demonstrates that the improvement in the selectivity toward gasoline range hydrocarbons is due to the acid‐catalyzed reactions of the Fischer–Tropsch α‐olefins over the acidic zeolite. The formation of methane over the zeolite‐supported Co catalysts originates from direct CO hydrogenation and hydrocarbon hydrogenolysis on coordinatively unsaturated Co sites, which are stabilized as a consequence of a strong metal–zeolite interaction. Although the addition of either ZrO2 or Ru increases the catalyst reducibility considerably, it does not affect the product selectivity significantly.

Electronic origins of photocatalytic activity in d 0 metal organic frameworks

Metal-organic frameworks (MOFs) containing d0 metals such as NH2-MIL-125(Ti), NH2-UiO-66(Zr) and NH2-UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH2-MIL-125(Ti) promote a long lived ligand-to-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d-orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π* orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids.

Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers

The reactivity of 2,5-dihydroxyterephthalic acid (H4DOBDC) with titanium(IV) precursors was thoroughly investigated for the synthesis of metal-organic frameworks under solvothermal conditions. Four crystalline phases were isolated whose structures were studied by a combination of single-crystal or powder X-ray diffraction and solid-state NMR. The strong coordination ability of the phenolate moieties was found to favor the formation of isolated TiO6 octahedra bearing solely organic ligands in the resulting structures, unless hydrothermal conditions and precondensed inorganic precursors are used. It is worth noting that these solids strongly absorb visible light, as a consequence of the ligand-to-metal charge transfer (LMCT) arising from Ti-phenolate bonds. Preliminary photocatalytic tests suggest that one compound, namely, MIL-167, presents a higher activity for hydrogen evolution than the titanium carboxylate MIL-125-NH2 but that such an effect cannot be directly correlated with its improved light absorption feature.

Organic Linker Defines the Excited-State Decay of Photocatalytic MIL-125(Ti)-Type Materials.

Recently, MIL-125(Ti) and NH2 -MIL-125(Ti), two titanium-based metal-organic frameworks, have attracted significant research attention in the field of photocatalysis for solar fuel generation. This work reveals that the differences between these structures are not only based on their light absorption range but also on the decay profile and topography of their excited states. In contrast to MIL-125(Ti), NH2 -MIL-125(Ti) shows markedly longer lifetimes of the charge-separated state, which improves photoconversion by the suppression of competing decay mechanisms. We used spectroelectrochemistry and ultrafast spectroscopy to demonstrate that upon photoexcitation in NH2 -MIL-125(Ti) the electron is located in the Ti-oxo clusters and the hole resides on the aminoterephthalate unit, specifically on the amino group. The results highlight the role of the amino group in NH2 -MIL-125(Ti), the electron donation of which extends the lifetime of the photoexcited state substantially.

Illuminating the nature and behavior of the active center: the key for photocatalytic H2 production in Co@NH2-MIL-125(Ti)

Advanced atomically resolved characterization methods unveil the mechanism of a promising photocatalytic Co@MOF(Ti) system for H2 production. The combination of X-ray absorption spectroscopy (XAS) and electron paramagnetic resonance (EPR) experiments allows for the characterization of atomic and electronic rearrangements in the photoinduced species. This information provides the basis for the optimization of photocatalyst design.

CHAPTER 8:Photocatalysis: Past Achievements and Future Trends

Photocatalysis holds great promise to enable sustainable chemical processes related to, for example, the production of renewable fuels or prevention of pollution through advanced oxidation. However, despite significant progress and continuing interest from academia, industry and policy makers, key challenges have to be overcome. First, ideal photocatalytic materials should obey stringent requirements related to stability, cost, bandgap compatibility, availability of raw materials, and photon efficiency. In spite of certain limitations, such as an undesirable band gap, titania remains the frontrunner in terms of research and commercial applications. This chapter briefly discusses strategies to expand the allowable bandgap of photocatalytic materials. A key focus is on the use of metal–organic frameworks (MOFs). MOFs have an organic–inorganic structure, exhibit a high surface area and can be tuned with tremendous flexibility, which makes them promising candidates to advance photocatalysis. Second, the development of photocatalytic reactors is discussed. The design and operation of photocatalytic reactors is not trivial due to requirements for efficient contact of reactants with the catalyst and efficient utilization of photons. The former requirement is common for any heterogeneous catalytic reactor whereas the latter is unique for photocatalysis. Consequently, numerous reactor configurations have been designed specifically for photocatalysis of which a selection is reviewed in this chapter. Recent advances in simulation and optimization of mathematical models of photocatalytic reactors offer an important support for design. Furthermore, novel solid-state light sources provide opportunities for increased robustness, reduced costs and improved flexibility for the design and operation of future photocatalytic reactors.