Visible-light-driven photocatalytic carboxylation to aromatic carboxylic acids with CO2.

(Hetero)aromatic carboxylic acids and their derivatives attract attention due to their role in the synthesis of several biologically active molecules, active pharmaceutical ingredients, polymers, etc. Carbon dioxide (CO2) is a prime C1 source for the synthesis of aromatic carboxylic acids because of its nontoxicity, nonflammability, abundance and renewability. Owing to the thermodynamic and chemical inertness of CO2, traditional carboxylation to aromatic carboxylic acids with CO2 is always performed under harsh reaction conditions or using stoichiometric metallic reductants. Visible-light-driven carboxylation with CO2 provides an environmentally benign, mild, and high-efficiency route for the production of aromatic carboxylic acids. This review comprehensively introduces the visible-light-driven preparation of aromatic carboxylic acids through a visible-light-driven oxidative addition and reductive elimination mechanism, binding of aryl (radical) anions which are produced by photoinduced electron transfer (PET) to CO2, binding of carbon dioxide anion radicals (CO2˙-) which are formed by PET to aryl compounds, radical coupling between CO2˙- and aryl radicals, and other mechanisms. Finally, this review provides a summary and the future work direction. This article offers a theoretical guidance for efficient synthesis of aromatic carboxylic acids via photocatalysis.

Construction of ZnO/Zn3In2S6/Pt with integrated S-scheme/Schottky heterojunctions for boosting photocatalytic hydrogen evolution and bisphenol a degradation.

Photocatalytic water splitting has been identified as a promising solution to tackle the current environmental and energy crisis in the world. However, the challenge of this green technology is the inefficient separation and utilization of photogenerated electron-hole pairs in photocatalysts. To overcome this challenge in one system, a ternary ZnO/Zn3In2S6/Pt material was prepared as a photocatalyst using a stepwise hydrothermal process and in-situ photoreduction deposition. The integrated S-scheme/Schottky heterojunction in the constructed ZnO/Zn3In2S6/Pt photocatalyst enabled it to exhibit efficient photoexcited charge separation/transfer. The evolved H2 reached up to 3.5 mmol g-1h-1. Meanwhile, the ternary composite possessed a high cyclic stability against photo-corrosion under irradiation. Practically, the ZnO/Zn3In2S6/Pt photocatalyst also showed great potential for H2 evolution while simultaneously degrading organic contaminants like bisphenol A. It is hoped in this work that the incorporation of Schottky junctions and S-scheme heterostructures in the construction of photocatalysts would lead to accelerated electron transfer and high photoinduced electron-hole pair separation, respectively, to synergistically enhance the performance of photocatalysts.

Photo-induced self-catalysis of nano-Bi2MoO6 for solar energy harvesting and charge storage.

Efficient, sustainable, and integrated energy systems require the development of novel multifunctional materials to simultaneously achieve solar energy harvesting and charge storage. Bi-based oxysalt aurivillius phase materials are potential candidates due to their typical photovoltaic effect and their pseudo-capacitance charge storage behavior. Herein, we synthesized nano-Bi2MoO6 as a material for both solar energy harvesting and charge storage due to its suitable band gap for absorption of visible light and its well-defined faradaic redox reaction from Bi metal to Bi3+. The irradiation of visible light significantly affected the electrochemical processes and the dynamics of the Bi2MoO6 electrode. The photo-induced self-catalytic redox mechanism was carefully explored by adding sacrificial agents in photocatalysis reaction. In accordance with the rule of energy matching, the photo-generated holes oxidized the Bi metal to Bi3+, and the corresponding peak current increased by 79.5% at a scanning rate of 50 mV s-1. More importantly, the peak current retention rate remained higher than 92.5% during the entire 200 cycles. The photo-generated electrons facilitated a decrease of 184 mV in the overpotential of the reduction process. Furthermore, the irradiation of visible light also accelerated the ionic diffusion of the electrolyte. These investigations provide a unique perspective for the design and development of new multifunctional materials to synergistically realize solar energy harvesting and charge storage.

A Bunch-Like Tertiary Amine Grafted Polysulfone Membrane for VRFBs with Simultaneously High Proton Conductivity and Low Vanadium Ion Permeability.

Novel polysulfone membranes with bunch-like tertiary amine groups are synthesized with high ion selectivity and outstanding chemical stability for vanadium redox flow batteries (VRFBs). The bunch-like tertiary amine groups simultaneously act as an ionic conductor for proton hopping and vanadium ion transport obstacles. The performance of the membrane is tuned via controlling the grafting degree of the chloromethylated polysulfone. The results show that membranes show increasing proton over vanadium ion (σ/p) selectivity with increasing functional tertiary groups. VRFBs assembled with the prepared membranes demonstrate an impressive Coulombic efficiency of 98.9% and energy efficiency of 90.9% at a current density of 50 mA cm-2 . Furthermore, the prepared membrane reported in this work shows excellent stability in 1 m VO2+ solution at 35 °C over 240 h. Overall, the synthesized polymers provide a new insight into the design of high-performance membranes toward VRFB applications.

A low-toxic artificial fluorescent glycoprotein can serve as an efficient cytoplasmic labeling in living cell.

To maintain the virtue of good optical property and discard the dross of conventional fluorescent staining dyes, we provide a strategy for designing new fluorescent scaffolds. In this study, a novel fluorescent labeling glycoprotein (chitosan-poly-L-cysteine, CPC) was synthesized through graft copolymerization. CPC gives emission peak at 465-470 nm when excited at 386 nm. The submicro-scale CPC microspheres could be localized and persisted specifically in the cytoplasm of living cells, with strong blue fluorescence. Moreover, CPC was highly resistant to photo bleaching, the fluorescence was remained stable for up to 72 h as the cells grew and developed. The glycoprotein CPC was bio-compatible and in zero grade cytotoxicity as quantified by MTT assay. The fluorescent labeling process with our newly designed glycoprotein CPC is exceptionally efficient.

A gemini quaternary ammonium poly (ether ether ketone) anion-exchange membrane for alkaline fuel cell: design, synthesis, and properties.

To reconcile the tradeoff between conductivity and dimensional stability in AEMs, a novel Gemini quaternary ammonium poly (ether ether ketone) (GQ-PEEK) membrane was designed and successfully synthesized by a green three-step procedure that included polycondensation, bromination, and quaternization. Gemini quaternary ammonium cation groups attached to the anti-swelling PEEK backbone improved the ionic conductivity of the membranes while undergoing only moderate swelling. The grafting degree (GD) of the GQ-PEEK significantly affected the properties of the membranes, including their ion-exchange capacity, water uptake, swelling, and ionic conductivity. Our GQ-PEEK membranes exhibited less swelling (≤ 40 % at 25-70 °C, GD 67 %) and greater ionic conductivity (44.8 mS cm(-1) at 75 °C, GD 67 %) compared with single quaternary ammonium poly (ether ether ketone). Enhanced fuel cell performance was achieved when the GQ-PEEK membranes were incorporated into H2 /O2 single cells.

In situ synthesis of nanocomposite membranes: comprehensive improvement strategy for direct methanol fuel cells.

In situ synthesis is a powerful approach to control nanoparticle formation and consequently confers extraordinary properties upon composite membranes relative to conventional doping methods. Herein, uniform nanoparticles of cesium hydrogen salts of phosphotungstic acid (CsPW) are controllably synthesized in situ in Nafion to form CsPW­Nafion nanocomposite membranes with both improved proton conductivity and methanol-crossover suppression. A 101.3% increase of maximum power density has been achieved relative to pristine Nafion in a direct methanol fuel cell (DMFC), indicating a potential pathway for large-scale fabrication of DMFC alternative membranes.