Visible light induced hydrogen generation using a hollow photocatalyst with two cocatalysts separated on two surface sides.

A hollow Fe2O3-TiO2-PtOx photocatalyst for visible light H2 generation was prepared from nanosized MIL-88B consisting of coordinatively unsaturated metal centers as a hard template. This photocatalyst is composed of hybrid metal oxide-TiO2 with controllable wall thickness and two different cocatalysts that are separately located on two surface sides.

Novel route to size-controlled Fe-MIL-88B-NH2 metal-organic framework nanocrystals.

A new approach for the synthesis of uniform metal-organic framework (MOF) nanocrystals with controlled sizes and aspect ratios has been developed using simultaneously the non-ionic triblock co-polymer F127 and acetic acid as stabilizing and deprotonating agents, respectively. The alkylene oxide segments of the triblock co-polymer can coordinate with metal ions and stabilize MOF nuclei in the early stage of the formation of MOF nanocrystals. Acetic acid can control the deprotonation of carboxylic linkers during the synthesis and, thus, enables the control of the rate of nucleation, leading to the tailoring of the size and aspect ratio (length/width) of nanocrystals. Fe-MIL-88B-NH(2), as an iron-based MOF crystal, was selected as a typical example to illustrate our approach. The results reveal that this approach is used for not only the synthesis of uniform nanocrystals but also the control of the size and aspect ratio of the materials. The size and aspect ratio of nanocrystals increase with an increase in the concentration of acetic acid in the synthetic mixture. The non-ionic triblock co-polymer F127 and acetic acid can be easily removed from the Fe-MIL-88B-NH(2) nanocrystal products by washing with ethanol, and thus, their amine groups are available for practical applications. The approach is expected to synthesize various nanosized carboxylate-based MOF members, such as MIL-53, MIL-89, MIL-100, and MIL-101.

In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework.

Chemical and physical transformations by milling are attracting enormous interest for their ability to access new materials and clean reactivity, and are central to a number of core industries, from mineral processing to pharmaceutical manufacturing. While continuous mechanical stress during milling is thought to create an environment supporting nonconventional reactivity and exotic intermediates, such speculations have remained without proof. Here we use in situ, real-time powder X-ray diffraction monitoring to discover and capture a metastable, novel-topology intermediate of a mechanochemical transformation. Monitoring the mechanochemical synthesis of an archetypal metal-organic framework ZIF-8 by in situ powder X-ray diffraction reveals unexpected amorphization, and on further milling recrystallization into a non-porous material via a metastable intermediate based on a previously unreported topology, herein named katsenite (kat). The discovery of this phase and topology provides direct evidence that milling transformations can involve short-lived, structurally unusual phases not yet accessed by conventional chemistry.

Design of multicomponent photocatalysts for hydrogen production under visible light using water-soluble titanate nanodisks.

We report the design of efficient multicomponent photocatalysts (MPs) for H2 production under visible light by using water-soluble ultrathin titanate nanodisks (TNDs) stabilized by tetraethylammonium cations (TEA(+)) as building blocks. The photocatalysts are designed in such a way to significantly enhance simultaneously the efficiency of the three main steps in the photocatalytic process i.e., light absorption, charge separation and catalytic reaction. We show, as an example, the construction of water-soluble CdS-TND-Ni MPs. The designed CdS-TND-Ni MPs, in which CdS nanoparticles and TNDs are intimately assembled to enhance the charge transfer and surface area, are controlled in composition to optimize visible light absorption. The conception of the MPs allows them to be highly dispersed in water which markedly improves the photocatalytic H2 production process. Most importantly, a Ni co-catalyst is selectively located on the surface of TNDs, enabling vectorial electron transfer from CdS to TND and to Ni, which drastically improves the charge separation. Consequently, under visible light illumination (λ ≥ 420 nm), the optimally designed CdS-TND-Ni MPs could generate H2 from ethanol-water solution with rate as high as 15.326 mmol g(-1) h(-1) during a reaction course of 15 h and with an apparent quantum yield of 24% at 420 nm. Moreover, we also demonstrate that TNDs can be combined with other single or mixed metal sulfide to form water-soluble metal sulfide-TNDs composites which could also be of great interest for photocatalytic H2 production.

Synthesis and engineering porosity of a mixed metal Fe2Ni MIL-88B metal-organic framework.

A new rational approach has been developed for the synthesis of a mixed metal MIL-88B metal-organic framework based on a neutral mixed metal cluster, such as Fe(2)Ni(µ(3)-O). Unlike the conventional negative charged single metal cluster, the use of the neutral mixed metal cluster as nodes in the framework avoids the need of a compensating anion inside the porous MIL-88B system; thus the mixed metal MIL-88B becomes porous. The flexibility of the mixed metal MIL-88B can be controlled by terminal ligands with different steric hindrance. This allows us to reversibly customize the porosity of the MIL-88B structure at three levels of specific surface area as well as the pore volume.