Hybrid Cu_<i>x</i>O–TiO₂ Heterostructured Composites for Photocatalytic CO₂ Reduction into Methane Using Solar Irradiation: Sunlight into Fuel

Photocatalytic CO₂ conversion to fuel offers an exciting prospect for solar energy storage and transportation thereof. Several photocatalysts have been employed for CO₂ photoreduction; the challenge of realizing a low-cost, readily synthesized photocorrosion-stable photocatalytic material that absorbs and successfully utilizes a broad portion of the solar spectrum energy is as yet unmet. Herein, a mesoporous p-type/n-type heterojunction material, Cu_<i>x</i>O–TiO₂ (<i>x</i> = 1, 2), is synthesized via annealing of Cu/Cu₂O nanocomposites mixed with a TiO₂ precursor (TiCl₄). Such an experimental approach in which two materials of diverse bandgaps are coupled provides a simultaneous opportunity for greater light absorption and rapid charge separation because of the intrinsic p–n heterojunction nature of the material. As detailed herein, this heterostructured photocatalyst demonstrates an improved photocatalytic activity. With the CO₂ reduction of our optimal sample (augmented light absorption, efficacious charge separation, and mesoporosity) that utilizes no metal cocatalysts, a remarkable methane yield of 221.63 ppm·g⁻¹·h⁻¹ is achieved

Elucidation of Active Sites and Mechanistic Pathways of a Heteropolyacid/Cu-Metal–Organic Framework Catalyst for Selective Oxidation of 5‑Hydroxymethylfurfural via Ex Situ X‑ray Absorption Spectroscopy and In Situ Attenuated Total Reflection-Infrared Studies

Chemoselective oxidation of 5-hydroxymethylfurfural (HMF) over non-noble metals to produce a bioplastic monomer, 2,5-furandicarboxylic acid (FDCA), under alkaline-free conditions is challenging and worthy of investigation. HMF oxidation into FDCA involves the concurrent oxidation of primary alcohol and an aldehyde functional group into carboxylic groups, which therefore demand a bifunctional catalyst containing dual active sites and chemoselective oxidation of HMF. The present work demonstrated the formation of new selective active sites in a composite porous material (Cu-BTC_PMA) that consists of Cu-BTC (metal–organic framework (MOF)) and polyoxometalate (POM). The porous framework provides (Cu-BTC_PMA) the desired chemoselectivity, while a selective Cu metal center in Cu-BTC (MOF) and Cu–O–Mo sites functions as active sites for the concurrent oxidation of HMF into FDCA. This catalyst exhibited a HMF conversion of 89% and an FDCA selectivity of 92.3% under base-free and mild reaction conditions. In detail, X-ray absorption spectroscopy analysis demonstrated the chemical bond tuning, as well as electronic structural modulations of MOF and POM at the molecular level, which directs the formation of new synergistic interfacial active sites and charge transfer states. This phenomenon causes the generation of the unique redox environment of copper and the multiple oxidation states along with the oxygen vacancy in the Cu-BTC_PMA catalyst, which most likely behaves as active sites for base-free oxidation. A kinetics study of this reaction was followed using in situ attenuated total reflection-infrared spectroscopy, demonstrating the stabilization of the specific intermediates that lead to the formation of FDCA. Moreover, we made comparative density functional theory and quantum theory of atoms in molecules investigations on the surface interaction between the reactant (HMF) and two catalyst models of Cu-BTC and Cu-BTC_PMA to interpret quantitatively the higher catalytic activity of the Cu-BTC_PMA catalyst. The kinetics study also evaluates the rate-determining step and activation energy for the multistep oxidation reactions

Highly Efficient Visible Blue-Emitting Black Phosphorus Quantum Dot: Mussel-Inspired Surface Functionalization for Bioapplications

The preparation of blue-emitting black phosphorus quantum dots (BPQDs) is based on the liquid-phase exfoliation of bulk BP. We report the synthesis of soluble BPQDs showing a strong visible blue-light emission. Highly fluorescent (photoluminescence quantum yield of ≈5% with the maximum emission (λ_max) at ≈437 nm) and dispersible BPQDs in various organic solvents are first prepared by simple ultrasonication of BP crystals in chloroform in the ambient atmosphere. Furthermore, simple mussel-inspired surface functionalization of BPQDs with catechol-grafted poly­(ethylene glycol) in basic buffer afforded water-soluble blue-emitting BPQDs showing long-term fluorescence stability, very low cytotoxicity, and excellent fluorescence live cell imaging capability