Photocatalytic Methanol Dehydrogenation with Switchable Selectivity.

Switchable selectivity achieved by altering reaction conditions within the same photocatalytic system offers great advantages for sustainable chemical transformations and renewable energy conversion. In this study, we investigate an efficient photocatalytic methanol dehydrogenation with controlled selectivity by varying the concentration of nickel cocatalyst, using zinc indium sulfide nanocrystals as a semiconductor photocatalyst, which enables the production of either formaldehyde or ethylene glycol with high selectivity. Control experiments revealed that formaldehyde is initially generated and can either serve as a terminal product or intermediate in producing ethylene glycol, depending on the nickel concentration in the solution.

High-Photovoltage Silicon Nanowire for Biological Cofactor Production.

Photocathodic conversion of NAD to NADH cofactor is a promising platform for activating redox biological catalysts and enzymatic synthesis using renewable solar energy. However, many photocathodes suffer from low photovoltage, consequently requiring a high cathodic bias for NADH production. Here, we report an np-type silicon nanowire (np-SiNW) photocathode having a photovoltage of 435 mV to drive energy-efficient NADH production.

Photochemical Diodes for Simultaneous Bias-Free Glycerol Valorization and Hydrogen Evolution.

Artificial photosynthesis offers a route to producing clean fuel energy. However, the large thermodynamic requirement for water splitting along with the corresponding sluggish kinetics for the oxygen evolution reaction (OER) limits its current practical application. Here, we offer an alternative approach by replacing the OER with the glycerol oxidation reaction (GOR) for value-added chemicals.

Controlling the Phase Transition in CsPbI Nanowires.

Cesium lead iodide (CsPbI) is a promising semiconductor with a suitable band gap for optoelectronic devices. CsPbI has a metastable perovskite phase that undergoes a phase transition into an unfavorable nonperovskite phase in an ambient environment. This phase transition changes the optoelectronic properties of CsPbI and hinders its potential for device applications.

Biocompatibility of NbTaTiVZr with Surface Modifications for Osteoblasts.

We report a potential biomedical material, NbTaTiVZr, and the impact of surface roughness on the osteoblast culture and later behavior based on in vitro tests of preosteoblasts. Cell activities such as adhesion, viability, and typical protein activity on NbTaTiVZr showed comparable results with that of commercially pure Ti (CP-Ti). In addition, NbTaTiVZr with a smooth surface exhibits better cell adhesion, viability, and typical protein activity which shows that surface modification can improve the biocompatibility of NbTaTiVZr.

Diversified Excited-State Relaxation Pathways of Donor-Linker-Acceptor Dyads Controlled by a Bent-to-Planar Motion of the Donor.

Herein, we introduce the cyclic 8π-electron (C8π) molecule N,N'-diaryl-dihydrodibenzo[a,c]phenazine (DPAC) as a dual-functional donor to establish a series of new donor-linker-acceptor (D-L-A) dyads DLA1-DLA5. The excited-state bent-to-planar dynamics of DPAC regulate the energy gap of the donor, while the acceptors A1-A5 are endowed with different energy gaps and HOMO/LUMO levels. As a result, the rate and efficiency of the excited-state electron transfer vs.

Mono-Heteroatom Substitution for Harnessing Excited-State Structural Planarization of Dihydrodibenzo[a,c]phenazines.

With the aim of generalizing the structure-properties relationship of bending heterocyclic molecules that undergo prominent photoinduced structural planarization (PISP), a series of new dihydrodibenzo[ac]phenazine derivatives in which one nitrogen atom is replaced by oxygen (PNO), sulfur (PNS), selenium (PNSe), or dimethylmethanediyl (PNC) was strategically designed and synthesized. Compounds PNO, PNS, and PNSe have significantly nonplanar geometries in the ground state, which undergo PISP to give a planarlike conformer and hence a large emission Stokes shift. A combination of femtosecond early relaxation dynamics and computational approaches established an R*→I* (intermediate)→P* sequential kinetic pattern for PNS and PNSe, whereas PNO undergoes R*→P* one-step kinetics.

Near-Infrared Emission Induced by Shortened Pt-Pt Contact: Diplatinum(II) Complexes with Pyridyl Pyrimidinato Cyclometalates.

Four diplatinum(II) complexes with the formula [Pt(pypm)(μ-F)] (, -) bearing both a pyridine-pyrimidinate chelate and formamidinate bridge, where (pypm)H and FH stand for 5-(pyridin-2-yl)-2-(trifluoromethyl)pyrimidine and functional formamidines with various substituents of Pr ( = 1), Ph ( = 2), CHBu ( = 3), and CHCF ( = 4), were synthesized en route from a mononuclear intermediate represented by [Pt(pypm)Cl(FH)] (). Single-crystal X-ray diffraction studies confirmed the structure of and comprised of an individual "Pt(pypm)" unit and two "Pt(pypm)" units with a Pt···Pt distance of 2.8845(2) Å, respectively.

Phenothiazine Scope: Steric Strain Induced Planarization and Excimer Formation.

Phenothiazine derivatives based on the 10-phenyl-10H-phenothiazine (NAS) chromophore, namely 7-phenyl-7H-benzo[c]phenothiazine (NAS-1) and 12-phenyl-12H-benzo[a]phenothiazine (NAS-2), were designed and synthesized. NAS-1 and NAS-2 are constitutional isomers with different steric strains imposed on the phenothiazine core moiety. In solution, the more-strained NAS-2 possesses a bent structure and undergoes photoinduced structural planarization (PISP).