利用原子层沉积法合成的硼掺杂二氧化硅支撑的 Pt Sites 对丙烷进行非氧化脱氢。

IF 1.3 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Turkish Journal of Chemistry Pub Date : 2023-12-04 eCollection Date: 2024-01-01 DOI:10.55730/1300-0527.3648
Gökhan Çelik
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引用次数: 0

摘要

使用铂基支撑催化剂将丙烷非氧化脱氢为丙烯是催化领域一个活跃的研究领域,因为铂位点的催化剂属性可以通过精心设计活性位点来控制。实现这一目标的方法之一是添加第二种金属,这种金属可能会改变活性位点的电子密度,进而影响催化性能。本研究利用原子层沉积(ALD)技术在粉末二氧化硅上沉积了双金属铂和硼位点。首先使用三异丙基硼酸盐作为硼源,通过半周期 ALD 在二氧化硅上沉积硼。煅烧后,使用三甲基(甲基环戊二烯基)铂(IV)作为铂源,通过半周期 ALD 进行铂沉积。合成的催化剂在 550 °C 的 H2 条件下进行还原,并使用电感耦合等离子体光发射光谱进行元素分析,使用吸附 CO 的漫反射红外傅立叶变换光谱检测铂的性质,以及使用时间分辨 X 射线吸收近边缘结构光谱检测铂位点还原性的变化。然后,利用固定床塞流反应器对样品进行了 550 °C 丙烷非氧化脱氢试验,以考察 B 对催化性能的影响。表征结果表明,硼的加入增加了电子密度,并影响了铂位点的还原性。此外,在二氧化硅上加入 B 还为铂的 ALD 创造了锚定位点。B/SiO2 上的铂沉积量是 SiO2 上的 2.2 倍。催化活性结果表明,B 的加入并没有显著改变铂位点的初始活性,但丙烯选择性从 80% 提高到 87%,稳定性提高了近三倍。PtB/SiO2 的选择性和稳定性的提高很可能是由于在反应条件下分别促进了丙烯的解吸和减少了焦炭的形成。
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Nonoxidative dehydrogenation of propane using boron-incorporated silica-supported Pt Sites synthesized by atomic layer deposition.

Nonoxidative dehydrogenation of propane to propylene using Pt-based supported catalysts is an active research area in catalysis because catalyst attributes of Pt sites can be controlled by careful design of active sites. One way to achieve this is by the addition of a second metal that may impart a change in the electron density of active sites, which in turn affects catalytic performance. In this study, bimetallic Pt and B sites were deposited on powder SiO2 using atomic layer deposition (ALD). Boron was first deposited on SiO2 via half-cycle ALD using triisoproplyborate as the B source. Following calcination, Pt deposition was performed via half-cycle ALD using trimethyl(methylcyclopentadienyl)platinum(IV) as the Pt source. The synthesized catalysts were reduced under H2 at 550 °C and characterized using inductively coupled plasma optical emission spectroscopy for elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy of adsorbed CO to examine the properties of Pt, and time-resolved X-ray absorption near edge structure spectroscopy to examine the changes in the reducibility of Pt sites. The samples were then tested for nonoxidative dehydrogenation of propane at 550 °C using a fixed-bed plug-flow reactor to examine the role of B on the catalytic performance. Characterization results showed that the addition of B imparted an increase in electron density and affected the reducibility of Pt sites. In addition, incorporating B on SiO2 created anchoring sites for Pt ALD. The amount of Pt deposited on B/SiO2 was 2.2 times that on SiO2. Catalytic activity results revealed the addition of B did not change the initial activity of Pt sites significantly, but improved propylene selectivity from 80% to 87% and stability almost threefold. The enhanced selectivity and stability of PtB/SiO2 is most presumably due to favored desorption of propylene and mitigating coke formation under reaction conditions, respectively.

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来源期刊
Turkish Journal of Chemistry
Turkish Journal of Chemistry 化学-工程:化工
CiteScore
2.40
自引率
7.10%
发文量
87
审稿时长
3 months
期刊介绍: The Turkish Journal of Chemistry is a bimonthly multidisciplinary journal published by the Scientific and Technological Research Council of Turkey (TÜBİTAK). The journal is dedicated to dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, polymeric, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences especially in chemical engineering where molecular aspects are key to the findings. The journal accepts English-language original manuscripts and contribution is open to researchers of all nationalities. The journal publishes refereed original papers, reviews, letters to editor and issues devoted to special fields. All manuscripts are peer-reviewed and electronic processing ensures accurate reproduction of text and data, plus publication times as short as possible.
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