Selective oxidation of aliphatic alcohols under mild and base-free conditions is a challenging process for organic synthesis. Herein, we report a one-pot process for the direct oxidative esterification of aliphatic alcohols that is significantly enhanced by visible-light irradiation at ambient temperatures. The new methodology uses heterogenerous photocatalysts of gold-palladium alloy nanoparticles on a phosphate-modified hydrotalcite support and molecular oxygen as a benign oxidant. The alloy photocatalysts can absorb incident light, and the light-excited metal electrons on the surface of metal nanoparticles can activate the adsorbed reactant molecules. Tuning the light intensity and wavelength of the irradiation can remarkably change the reaction activity. Shorter wavelength light (<550 nm) drives the reaction more efficiently than light of longer wavelength (e.g., 620 nm), especially at low temperatures. The phosphate-exchanged hydrotalcite support provides sufficient basicity (and buffer) for the catalytic reactions; thus, the addition of base is not required. The photocatalysts are efficient and readily recyclable. The findings reveal the first example of using "green" oxidants and light energy to drive direct oxidative esterification of aliphatic alcohols under base-free, mild conditions.

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Here we report a class of photocatalysts: mixed-valence vanadium oxide particles grafted onto a variety of oxide supports. In these catalysts V6O13 species with mixed oxidation states (V4+ or V5+) are believed to be catalytically active sites. These catalysts successfully enable alcohol oxidation to selectively produce aldehydes and ketones using O2 as the oxidant. The catalytic process is driven by visible light irradiation at room temperature and, most importantly, progresses with negligible overoxidation. The catalysts can even selectively oxidize aliphatic alcohols, which are much more challenging to control in comparison to aromatic analogues. They can also be applied to the activation and oxidation of the otherwise stable C–H bonds of saturated aromatic hydrocarbons, such as toluene and xylene, under irradiation. Both experimental results and density functional theory (DFT) simulations suggest the formation of V6O13-alkoxide species as the initial step in the catalytic cycle. The V6O13-alkoxide then acts as the light harvester, being excited by light of wavelength shorter than 550 nm. Facile room-temperature C–H bond cleavage in the excited state V6O13-alkoxide in the presence of O2 leads to the carbonyl-containing products. These findings demonstrate an example of light-driven selective oxidation of diverse alcohols via in situ formation of photoresponsive V6O13-alkoxide species. This catalytic process is especially valuable for the synthesis of temperature-sensitive products and represents an alternative pathway to many conventional thermal oxidation reactions.

Scheme 1. Illustration of the Ti 3 C 2 T X MXene structure and its modification with Pt nanoparticles with and without employment of the reducing agent NaBH 4 .

In this paper, we propose and investigate an original approach to energy conversion based on polyzwitterionic hydrogels, which exhibit an antipolyelectrolyte effect that enables them to swell in salt water and shrink in water of a different (i.e., desalinated water) salinity. The swelling and shrinking processes run cyclically and can move a piston up or down reversibly, thus transforming the antipolyelectrolyte effect into a mechanical force based on the salinity gradient. This phenomenon makes polyzwitterionic hydrogels suitable for use in a smart, polymeric engine. We apply this approach to investigate energy recovery from a polysulfobetaine-based hydrogel. The cross-linking density, external load, particle size, and repeatability of energy recoverability of hydrogels are examined. The maximum energy recovery from 0.4 g of hydrogel in feed (calculated based on dry form) of 102 mJ/kg was obtained by a hydrogel with a 3% cross-linking density, a 200–300 μm particle size, and 100 g external load. Excellent reproducibility of engine cycles was achieved over 10 cycles. This concept is complementary to the osmotic engine concept based on a polyelectrolyte hydrogel. In addition, polyzwitterionic materials have become a benchmark material for preventing biofouling, and the swelling properties of such materials can be further modulated and tuned.