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Electrocatalytic oxidation of glycerol, an oversupplied byproduct of the biodiesel industry, into high‐valued chemicals is alluring to diminishing current dependence on fossil energy. Formic acid is an important glycerol oxidation product that serves as a high‐energy‐density fuel and crucial precursor for the fine chemical industry while developing an electrocatalyst to efficiently convert glycerol into formic acid remains a challenge. Herein, a Cu‐doped nickel phosphide (CuxNi2–xP) electrocatalyst, achieving formate productivity of ≈11 mol m−2 h−1 at 1.54 V versus RHE over a broad glycerol concentration range (10–100 mm) is reported, which is greater than threefolds than that of Ni2P. Furthermore, CuxNi2–xP can enhance the cleavage of C─C bond in glycerol, reducing the production of intermediates and thus attaining high selectivity of formate. In situ experiments integrated with density functional theory (DFT) calculation revealed that the doping of Cu can promote the generation of NiIII─OOH species and enrich glycerol substrates in local environments on CuxNi2–xP surface, thus facilitating reaction efficiency. Finally, the study designed a membrane‐free flow electrolyzer for continuous upgrading glycerol to formate, attaining 16.4 mmol of formate coupled with 0.68 L of H2 at 1.75 V in 8 h. [ABSTRACT FROM AUTHOR]

It is still a challenge to develop electrocatalyst for the efficient adsorption and conversion of organic molecule in aqueous media. Herein, a hetero‐interface structure based on CuO@Ni(OH)2 is rationally designed to enhance the performance of benzyl alcohol oxidation to benzoic acid. A high Faradaic efficiency of 99% and the yield of 3.09 mmol cm−2 h−1 are achieved at 1.70 V versus reversible hydrogen electrode, outperforming the previously reported electrocatalysts. Furthermore, a membrane‐free flow electrolyzer was assembled based on CuO@Ni(OH)2 hetero‐interface, exhibiting a much high yielding of benzoic acid (6.73 mmol cm−2 h−1) and hydrogen (0.35 L cm−2 h−1) with excellent stability. Both experimental data and density functional theory calculations verify that the electron is tend to accumulate at the hetero‐interface, thus accelerating the adsorption of reactant and intermediate and reducing the energy barrier of the conversion of benzyl alcohol to benzoic acid. [ABSTRACT FROM AUTHOR]

The electrochemical oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2O2) is appealing due to its sustainability. However, its efficiency is compromised by the competing 4e− ORR pathway. In this work, we report a hierarchical carbon nanosheet array electrode with a single-atom Ni catalyst synthesized using organic molecule-intercalated layered double hydroxides as precursors. The electrode exhibits excellent 2e− ORR performance under alkaline conditions and achieves H2O2 yield rates of 0.73 mol gcat−1 h−1 in the H-cell and 5.48 mol gcat−1 h−1 in the flow cell, outperforming most reported catalysts. The experimental results show that the Ni atoms selectively adsorb O2, while carbon nanosheets generate reactive hydrogen species, synergistically enhancing H2O2 production. Furthermore, a coupling reaction system integrating the 2e− ORR with ethylene glycol oxidation significantly enhances H2O2 yield rate to 7.30 mol gcat−1 h−1 while producing valuable glycolic acid. Moreover, we convert alkaline electrolyte containing H2O2 directly into the downstream product sodium perborate to reduce the separation cost further. Techno-economic analysis validates the economic viability of this system. Electrochemical oxygen reduction is a promising method for H2O2 production but suffers from poor activity and low yield. In this work, the authors present Ni single atom catalyst for efficient H2O2 production which is further coupled with organic oxidation reaction to enhance the economic feasibility of the system. [ABSTRACT FROM AUTHOR]

Phosphorus is widely present in living organisms and nature and exists in a variety of isomers with variable crystal structures. There are several common phosphorus monomers in biomedicine, including red phosphorus (RP), black phosphorus (BLK-P), violet phosphorus (VP), and blue phosphorus (BLU-P). Phosphorus-based semiconductor materials (PSCM) have adjustable band gaps, high photogenerated carrier mobility, and efficient photothermal conversion as well as good biocompatibility and degradability. In addition, phosphorus, an essential element for life-sustaining activities, is present in all cells of the human body, accounting for approximately 1% of the body's total weight. Therefore, phosphorus-based nanomaterials have extensive applications in the biomedical field. This review will clarify the classification, preparation methods, physicochemical properties, mechanisms of action, and applications in biomedicine of phosphorus-based nanomaterials while also offering new ideas for their development in biomedicine. [ABSTRACT FROM AUTHOR]

Utilizing sustainable electrocatalysis to upcycle glycerol (GLY; the by‐product of biodiesel) to lactic acid (LA; the key monomers for biodegradable polymer) is an efficient way to reduce the cost of biodiesel, which is also consistent with the waste‐to‐wealth principle. However, current research still suffers from issues of low LA selectivity (<80%), especially at high current density. Herein, we designed a cooperative catalyst by modifying BiOx nanolayers on gold nanoparticles (BiOx/Au), achieving high LA selectivity (82%) at high current density (226 mA cm−2 at 1.05 V vs. RHE), outperforming most of the reported works in the literature. We reveal that BiOx could promote the adsorption of the middle hydroxyl of GLY, which facilitates the formation of DHA and thus enables high LA selectivity. Moreover, the electron‐deficient Au in BiOx/Au is responsible for the enhanced current density, which is more beneficial to generate reactive oxygen species (OH*). To further reveal the application potential of this electrocatalytic strategy, we realized that the conversion of crude GLY extracted from cooking oil to LA coupled with H2 production using a membrane‐free flow electrolyzer, demonstrating a sustainable fashion to convert biodiesel waste into high value‐added product and H2 fuel. [ABSTRACT FROM AUTHOR]

The catalytic oxidation of glycerol, a surplus byproduct of biodiesel, has received increasing attention due to the popular applications of its oxidation products, such as aldehydes, ketones, and carboxylates. Photoelectrochemical (PEC) methods provide a clean and sustainable pathway for glycerol oxidation and upgrading. However, selective oxidation of glycerol is a challenge due to its complex oxidation path, where the cleavage of C−O or C−C bonds at different positions can lead to a variety of products. This concept aims to describe the recent advances in PEC selective glycerol oxidation for the preparation of multiple high value‐added products, and discuss the reaction mechanism and selective production strategies in detail. Finally, the remaining challenges and future prospects for the PEC glycerol oxidation system are presented. [ABSTRACT FROM AUTHOR]