Cu-Bi Bimetallic Catalysts Derived from Metal-Organic Framework Arrays on Copper Foam for Efficient Glycine Electrosynthesis.

Glycine as one of the most abundant amino acids in human proteins, with extensive applications in both life and industry, is conventionally synthesized through complex procedures or toxic feedstocks. In this study, we present a facile and benign electrochemical pathway for synthesis of glycine through reductive coupling of glyoxylic acid and nitrate over a copper-bismuth bimetal catalyst derived from a metal-organic framework (MOF) array on copper foam (Cu/Bi-C@CF). Remarkably, Cu/Bi-C@CF achieves a fantastic selectivity of 89%, corresponding a high Faraday efficiency of 65.9%. From control experiments, introduction of Bi caused the binding energy of Cu shift to lower state, which leads to a high selectivity towards the formation of key hydroxylamine intermediate rather than ammonia product, facilitating the formation of oxime and providing additional sites for subsequent hydrogenation reaction on the way to glycine. Moreover, the MOF array derivation ensures the effective dispersion of Bi and enhances the stability of Cu/Bi-C@CF. This innovative approach not only presents sustainable pathways for the production of value-added organonitrogen compounds utilizing readily available carbon and nitrogen sources, but also provides novel insights into the design of multistage structural catalysts for sequential reactions.

Highly Efficient One-pot Electrosynthesis of Oxime Ethers from NOx over Ultrafine MgO Nanoparticles Derived from Mg-based Metal-Organic Frameworks.

Oxime ethers are attractive compounds in medicinal scaffolds due to the biological and pharmaceutical properties, however, the crucial and widespread step of industrial oxime formation using explosive hydroxylamine (NH2OH) is insecure and troublesome. Herein, we present a convenient method of oxime ether synthesis in a one-pot tandem electrochemical system using magnesium based metal-organic framework-derived magnesium oxide anchoring in self-supporting carbon nanofiber membrane catalyst (MgO-SCM), the in situ produced NH2OH from nitrogen oxides electrocatalytic reduction coupled with aldehyde to produce 4-cyanobenzaldoxime with a selectivity of 93 % and Faraday efficiency up to 65.1 %, which further reacted with benzyl bromide to directly give oxime ether precipitate with a purity of 97 % by convenient filtering separation. The high efficiency was attributed to the ultrafine MgO nanoparticles in MgO-SCM, effectively inhibiting hydrogen evolution reaction and accelerating the production of NH2OH, which rapidly attacked carbonyl of aldehydes to form oximes, but hardly crossed the hydrogenation barrier of forming amines, thus leading to a high yield of oxime ether when coupling benzyl bromide nucleophilic reaction. This work highlights the importance of kinetic control in complex electrosynthetic organonitrogen system and demonstrates a green and safe alternative method for synthesis of organic nitrogen drug molecules.

Electrocatalytic Systems for NOx Valorization in Organonitrogen Synthesis.

Inorganic nitrogen oxide (NOx ) species, such as NO, NO2 , NO3 - , NO2 - generated from the decomposition of organic matters, volcanic eruptions and lightning activated nitrogen, play important roles in the nitrogen cycle system and exploring the origin of life. Meanwhile, excessive emission of NOx gases and residues from industry and transportation causes troubling problems to the environment and human health. How to efficiently handle these wastes is a global problem. In response to the growing demand for sustainability, scientists are actively pursuing sustainable electrochemical technologies powered by renewable energy sources and efficient utilization of hydrogen energy to convert NOx species into high-value organonitrogen chemicals. In this minireview, recent advances of electrocatalytic systems for NOx species valorization in organonitrogen synthesis are classified and described, such as amino acids, amide, urea, oximes, nitrile etc., that have been widely applied in medicine, life science and agriculture. Additionally, the current challenges including multiple side reactions and complicated paths, viable solutions along with future directions ahead in this field are also proposed. The coupling electrocatalytic systems provide a green mode for fixing nitrogen cycle bacteria and bring enlightenment to human sustainable development.

Electrocatalytic Synthesis of Pyridine Oximes using in Situ Generated NH2 OH from NO species on Nanofiber Membranes Derived from NH2 -MIL-53(Al).

Pyridine oximes produced from aldehyde or ketone with hydroxylamine (NH2 OH) have been widely applied in pharmaceutics, enzymatic and sterilization. However, the important raw material NH2 OH exhibits corrosive and unstable properties, leading to substantial energy consumption during storage and transportation. Herein, this work presents a novel method for directly synthesizing highly valuable pyridine oximes using in situ generated NH2 OH from electrocatalytic NO reduction with well-design nanofiber membranes (Al-NFM) derived from NH2 -MIL-53(Al). Particularly, 2-pyridinealdoxime, the precursor of antidote pralidoxime (2-PAM) for nerve agents suffering from scarcity and high cost, was achieved with a Faraday efficiency up to 49.8 % and a yield of 92.1 %, attributing to the high selectivity of NH2 OH production on Al-NFM, further easily reacted with iodomethane to produce 2-PAM. This study proposes a creative approach, having wide universality for synthesizing pyridine and other oximes with a range of functional groups, which not only facilitates the conversion of exhaust gas (NO) and waste water (NO2 - ) into valuable chemicals especially NH2 OH production and in situ utilization through electrochemistry, but also holds significant potential for synthesis of neuro detoxifying drugs to humanity security.

Electrosynthesis of α-Amino Acids from NO and other NOx species over CoFe alloy-decorated Self-standing Carbon Fiber Membranes.

The conversion of industrial exhaust gases of nitrogen oxides into high-value products is significantly meaningful for global environment and human health. And green synthesis of amino acids is vital for biomedical research and sustainable development of mankind. Herein, we demonstrate an innovative approach for converting nitric oxide (NO) to a series of α-amino acids (over 13 kinds) through electrosynthesis with α-keto acids over self-standing carbon fiber membrane with CoFe alloy. The essential leucine exhibits a high yield of 115.4 µmol h-1 corresponding a Faradaic efficiency of 32.4 %, and gram yield of products can be obtained within 24 hours in lab as well as an ultra-long stability (>240 h) of the membrane catalyst, which could convert NO into NH2 OH rapidly attacking α-keto acid and subsequent hydrogenation to form amino acid. In addition, this method is also suitable for other nitrogen sources including gaseous NO2 or liquidus NO3 - and NO2 - . Therefore, this work not only presents promising prospects for converting nitrogen oxides from exhaust gas and nitrate-laden waste water into high-value products, but also has significant implications for synthetizing amino acids in biomedical and catalytic science.