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钴钨酸氢氧水合物(CTOHH)在 DNA 支架上:用于氧气析出反应(OER)和芳香醇氧化的优异双功能催化剂。

Cobalt tungsten oxide hydroxide hydrate (CTOHH) on DNA scaffold: an excellent bi-functional catalyst for oxygen evolution reaction (OER) and aromatic alcohol oxidation.

机构信息

Academy of Scientific and Innovative Research (AcSIR), CSIR-Central Electrochemical Research Institute (CECRI) Campus, New Delhi, India.

Department of Chemistry, Indian Institute of Technology Madras, Chennai-600036, India.

出版信息

Dalton Trans. 2019 Dec 7;48(45):17117-17131. doi: 10.1039/c9dt03941d. Epub 2019 Nov 11.

Abstract

A material with interdisciplinary properties is of wide interest for use in environmental applications. Currently, hydrogen generation by electrolysis and formation of carbonyl derivatives from alcohols are two different fields that focus on energy and environmental applications. In this work, a new material, Cobalt Tungsten Oxide Hydroxide Hydrate (CTOHH) on deoxyribonucleic acid (DNA) scaffold having chain-like morphology has been prepared for the first time by a facile microwave heating method. The same CTOHH was also prepared without the DNA scaffold and resulted in irregular aggregated molecular structures. Further, both CTOHH-DNA and CTOHH were converted into CoWO-DNA and CoWO, respectively by annealing them at a temperature of 600 °C. All the four catalysts were used for electrocatalytic oxygen evolution reaction (OER) and for oxidation of aromatic alcohols. In OER, CTOHH-DNA delivered fruitful results compared to all other electrocatalysts. For attaining a current density of 10 mA cm, it just required an overpotential of 355 mV with a Tafel slope value of 47.5 mV dec. Similarly, all four catalysts were also analyzed for selective and controlled oxidation of aromatic alcohols to their respective aldehydes and ketones using molecular oxygen as a green oxidant where CTOHH-DNA showed better results. Chemo-selectivity has been observed for CTOHH-DNA in the co-presence of hydroxyl and cyano functional groups. The durability of CTOHH-DNA was analyzed and it showed excellent catalytic activity retention up to five cycles.

摘要

具有跨学科性质的材料在环境应用中受到广泛关注。目前,通过电解产生氢气和从醇类形成羰基衍生物是两个不同的专注于能源和环境应用的领域。在这项工作中,首次通过简便的微波加热方法在脱氧核糖核酸 (DNA) 支架上制备了具有链状形态的新型材料,即钴钨氧化物氢氧化物水合物 (CTOHH)。同样的 CTOHH 也没有 DNA 支架,得到的是不规则聚集的分子结构。此外,通过在 600°C 下退火,将 CTOHH-DNA 和 CTOHH 分别转化为 CoWO-DNA 和 CoWO。这四种催化剂都用于电催化氧气析出反应 (OER) 和芳香醇的氧化。在 OER 中,与所有其他电催化剂相比,CTOHH-DNA 产生了丰硕的结果。为了达到 10 mA cm 的电流密度,它只需要 355 mV 的过电势,塔菲尔斜率值为 47.5 mV dec。同样,使用分子氧作为绿色氧化剂,对所有四种催化剂也进行了分析,以选择性和可控氧化芳香醇为相应的醛和酮,其中 CTOHH-DNA 表现出更好的结果。在羟基和氰基官能团共存的情况下,CTOHH-DNA 表现出化学选择性。分析了 CTOHH-DNA 的耐用性,结果表明它在五个循环中保持了出色的催化活性。

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