氧化锌纳米粉体表面对 β-二酮的吸附:吸附物对二酮结构的依赖性

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL
Sanuthmi Dunuwila , Shi Bai , Caitlin M. Quinn , Mitchell S. Chinn , Andrew V. Teplyakov
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引用次数: 0

摘要

通过表面改性可以控制氧化物表面的化学、机械和电子特性。氧化锌纳米材料上 β-二酮的表面化学性质为研究吸附结构对二酮类型的依赖性,特别是对供电子和吸电子官能团的依赖性提供了机会。本研究通过光谱和计算方法研究了 1,1,1-三氟-2,4-戊二酮(三氟乙酰丙酮,tfacH)和 1,1,1,5,5,5-六氟-2,4-戊二酮(六氟乙酰丙酮,hfacH)在氧化锌纳米粉体上的吸附情况。尽管在气相中,hfacH 的烯醇结构占主导地位,而 tfacH 则存在大量的二酮,但一旦这些化合物被吸附到 ZnO 上,hfacH 的二酮酸酯就会成为大部分的表面物种,而 tfacH 则以离解的烯醇为主。此外,鉴于氧化锌的两性性质,有人提出,在碱性氧化物表面上,烯醇形式的 O-H 解离可能会推动 hfacH 完成解离,通过比较 hfacH 在氧化锌和氧化镁表面上的化学性质,这一提议得到了证实。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Adsorption of β-diketones on a surface of ZnO nanopowder: Dependence of the adsorbate on the diketone structure

Adsorption of β-diketones on a surface of ZnO nanopowder: Dependence of the adsorbate on the diketone structure

Surface modification has been established to control chemical, mechanical, and electronic properties of oxide surfaces. Surface chemistry of β-diketones on ZnO nanomaterials presents an opportunity to investigate the dependence of the adsorbate structure on the type of diketone and, specifically, on the presence of electron-donating and electron-withdrawing functional groups. This work compares the adsorption of 1,1,1-trifluoro-2,4-pentane-dione (trifluoroacetylacetone, tfacH) and 1,1,1,5,5,5-hexafluoro-2,4-pentane-dione (hexafluoroacetylacetone, hfacH) on ZnO nanopowder by interrogating the molecular structure of adsorbates with spectroscopic and computational methods. Despite the fact that in the gas phase the enol structure dominates for hfacH and the diketone has substantial presence for tfacH, once these compounds are adsorbed on ZnO, the diketonate is the majority of surface species for hfacH and dissociated enolate is dominant for tfacH. Moreover, given the amphoteric nature of ZnO, it is proposed that on a surface of basic oxide, the O-H dissociation of the enol form could be driven to completion for hfacH, and this proposal is confirmed by comparing chemistry of hfacH on ZnO and MgO surfaces.

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来源期刊
Surface Science
Surface Science 化学-物理:凝聚态物理
CiteScore
3.30
自引率
5.30%
发文量
137
审稿时长
25 days
期刊介绍: Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to: • model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions • nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena • reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization • phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization • surface reactivity for environmental protection and pollution remediation • interactions at surfaces of soft matter, including polymers and biomaterials. Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.
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