Stability and degradation of (oxy)nitride photocatalysts for solar water splitting.

Advancing towards alternative technologies for the sustainable production of hydrogen is a necessity for the successful integration of this potentially green fuel in the future. Photocatalytic and photoelectrochemical water splitting are promising concepts in this context. Over the past decades, researchers have successfully explored several materials classes, such as oxides, nitrides, and oxynitrides, in their quest for suitable photocatalysts with a focus on reaching higher efficiencies. However, to pave the way towards practicability, understanding degradation processes and reaching stability is essential, a domain where research has been scarcer. This perspective aims at providing an overview on recent progress concerning stability and degradation with a focus on (oxy)nitride photocatalysts and at providing insights into the opportunities and challenges coming along with the investigation of degradation processes and the attempts to improve the stability of photocatalysts.

Circumventing the Theoretical Scaling Relation Limit for the Oxygen Evolution Reaction.

Transition metal hydr(oxy)oxides (TMHs) are considered efficient electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. Toward identification of potential descriptors to circumvent the scaling relation limit for the OER, first-principles calculations were used to quantify the effects on the overpotential of different s (Mg), p (Al), and d (Ti, V, Cr, Fe, Co, Sc, and Zn) electron dopants in Ni-based TMHs. Both the adsorbate evolution mechanism (AEM) and the lattice oxygen-mediated mechanism (LOM) were examined. The results demonstrate that the formation energy of oxygen vacancies (EVO) is strongly affected by the chemical nature of the dopants. A linear relationship is identified between EVO and the free energy difference for the oxygen-oxygen coupling. A descriptor could be employed to discriminate whether the LOM is energetically favored over the AEM. These findings fill existing gaps in appropriate yet computationally light descriptors for direct identification between the AEM and LOM.

A ratiometric fluorescence platform based on WS2 QDs/CoOOH nanosheet system for α-glucosidase activity detection.

In this study, we have constructed a ratiometric fluorescence sensor for sensitive sensing of α-glucosidase activity based on WS2 QDs/ CoOOH nanosheet system. In this system, as an oxidase-imimicking nanomaterial, CoOOH nanosheet could convert o-phenylenediamine into 2,3-diaminophenazine (DAP), which had a high fluorescence emission at 575 nm. The DAP subsequently could quench the fluorescence of WS2 QDs via the inner filter effect (IFE). L-Ascorbic acid-2-O-α-D-glucopyranose could be hydrolyzed by α-glucosidase to yield ascorbic acid. CoOOH nanosheet can be converted to Co2+ ions by ascorbic acid, leading to the fluorescence decrease of DAP and the fluorescence recovery of WS2 QDs. Therefore, a novel ratio fluorescence sensing strategy was established for α-glucosidase detection based on WS2 QDs/CoOOH nanosheet system. This WS2 QDs/CoOOH nanosheet system has a low detection limit of 0.009 U/mL for α-Glu assay. The proposed strategy succeeded in detecting α-Glu in human serum samples.

Amorphous Domains in Black Titanium Dioxide.

Although oxygen vacancies (Ov s) play a critical role for many applications of metal oxides, a controllable synthetic strategy for anisotropic Ov s remains a great challenge. Here, a novel strategy is proposed to achieve the regional dual structure with anisotropic Ov s at both the surface and in the interior of TiO2 by constructing amorphous domains. The as-prepared black TiO2 with amorphous domains exhibits superior activity in degrading rhodamine B (RhB) solutions, which can instantly decompose RhB with just a shake. First-principle simulations reveal that subsurface Ov s in TiO2 are energetically favored, resulting in the formation of amorphous domains in the interior region via diffusion of surface-formed Ov s into the subsurface. The stable Ov -induced amorphous domains in TiO2 with enhanced catalytic performances provide a scalable strategy to practical Ov engineering in functional metal oxides.

Solid wetting-layers in inorganic nano-reactors: the water in imogolite nanotube case.

By combined use of wide-angle X-ray scattering, thermo-gravimetric analysis, inelastic neutron scattering, density functional theory and density functional theory molecular dynamics simulations, we investigate the structure, dynamics and stability of the water wetting-layer in single-walled aluminogermanate imogolite nanotubes (SW Ge-INTs): an archetypal system for synthetically controllable and monodisperse nano-reactors. We demonstrate that the water wetting-layer is strongly bound and solid-like up to 300 K under atmospheric pressure, with dynamics markedly different from that of bulk water. Atomic-scale characterisation of the wetting-layer reveals organisation of the H2O molecules in a curved triangular sublattice stabilised by the formation of three H-bonds to the nanotube's inner surface, with covalent interactions sufficiently strong to promote energetically favourable decoupling of the H2O molecules in the adlayer. The evidenced changes in the local composition, structure, electrostatics and dynamics of the Ge-INT's inner surface upon the formation of the solid wetting-layer demonstrate solvent-mediated functionalisation of the nanotube's cavity at room temperature and pressure, suggesting new strategies for the design of nano-rectors towards potential control of chemical reactivity in nano-confined volumes.

A General Strategy for Fabricating Isolated Single Metal Atomic Site Catalysts in Y Zeolite.

Exploring high-performance zeolite-supported metal catalysts is of great significance. Herein, we develop a strategy for fabricating isolated single metal atomic site catalysts in Y zeolite (M-ISAS@Y, M = Pt, Pd, Ru, Rh, Co, Ni, Cu) by in situ separating and confining a metal-ethanediamine complex into ß-cages during the crystallization process followed by thermal treatment. The M-ISAS are stabilized by skeletal oxygens of Y zeolite, and the crystallinity, porosity, and large surface area are well inherited in M-ISAS@Y. As a demonstration, acidic Pt-ISAS@Y is used for n-hexane isomerization involving consecutive catalytic dehydrogenation/hydrogenation on Pt-ISAS and isomerization on Brønsted acid sites. The turnover frequency value of Pt-ISAS reaches 727 h-1, 5 times more than Pt nanoparticles (∼3.5 nm), with a total isomer selectivity of more than 98%. This strategy provides a convenient route to fabricate promising zeolite-based M-ISAS catalysts for industrial applications.

Structural resolution of inorganic nanotubes with complex stoichiometry.

Determination of the atomic structure of inorganic single-walled nanotubes with complex stoichiometry remains elusive due to the too many atomic coordinates to be fitted with respect to X-ray diffractograms inherently exhibiting rather broad features. Here we introduce a methodology to reduce the number of fitted variables and enable resolution of the atomic structure for inorganic nanotubes with complex stoichiometry. We apply it to recently synthesized methylated aluminosilicate and aluminogermanate imogolite nanotubes of nominal composition (OH)3Al2O3Si(Ge)CH3. Fitting of X-ray scattering diagrams, supported by Density Functional Theory simulations, reveals an unexpected rolling mode for these systems. The transferability of the approach opens up for improved understanding of structure-property relationships of inorganic nanotubes to the benefit of fundamental and applicative research in these systems.