發(fā)布時(shí)間：2018-04-20 16:11

  本文選題：金屬催化 + 團(tuán)簇��； 參考：《催化學(xué)報(bào)》2017年09期

【摘要】：金屬催化劑在工業(yè)、環(huán)境、能源以及生物等過(guò)程具有重要的應(yīng)用.設(shè)計(jì)具有特定活性、環(huán)境友好型以及室溫下具有反應(yīng)活性的催化劑,需要在分子水平對(duì)金屬催化劑的基元步驟,活性位點(diǎn)的結(jié)構(gòu)以及催化反應(yīng)微觀機(jī)理有充分的認(rèn)識(shí).然而,由于宏觀催化劑表面結(jié)構(gòu)異常復(fù)雜,催化反應(yīng)常受到溶劑、壓力、金屬顆粒團(tuán)聚、催化劑表面缺陷等因素的干擾,利用現(xiàn)有實(shí)驗(yàn)儀器,從微觀角度探索金屬催化反應(yīng)機(jī)理仍具有較大挑戰(zhàn),因此,對(duì)金屬催化劑活性位的結(jié)構(gòu)以及反應(yīng)微觀機(jī)理的認(rèn)識(shí)還不十分清楚.質(zhì)譜方法結(jié)合現(xiàn)代量子化學(xué)理論計(jì)算,提供了在氣相條件下實(shí)驗(yàn)探索化學(xué)反應(yīng)微觀機(jī)理的有力工具,團(tuán)簇反應(yīng)可在隔離外界條件、可控以及可重復(fù)條件下進(jìn)行,可以排除一些難以控制因素的干擾,可在化學(xué)鍵和分子結(jié)構(gòu)水平認(rèn)識(shí)金屬活性位的結(jié)構(gòu)以及催化反應(yīng)的微觀機(jī)理.氣相金屬團(tuán)簇離子可用多種實(shí)驗(yàn)方法制備,與反應(yīng)物分子反應(yīng)后可利用多種質(zhì)譜儀器探測(cè),根據(jù)實(shí)驗(yàn)上所得的具有反應(yīng)活性的團(tuán)簇,結(jié)合現(xiàn)代量子化學(xué)理論模擬,得到金屬催化反應(yīng)的基元步驟以及微觀反應(yīng)機(jī)理信息,所得反應(yīng)機(jī)理信息為宏觀催化劑的設(shè)計(jì)提供重要理論研究基礎(chǔ).本綜述總結(jié)了團(tuán)簇實(shí)驗(yàn)上已經(jīng)探測(cè)到的金屬單原子離子、金屬團(tuán)簇、金屬氧化物團(tuán)簇和金屬化合物催化的氣相反應(yīng).反應(yīng)物分子囊括了大量的無(wú)機(jī)和有機(jī)分子,包括CO,H_2,CH_4,C_2H_2,C_2H_4,C_6H_6,CH_3OH,HCOOH,CH_3COOH等.本綜述主要介紹了以下三類催化反應(yīng):(1)CO催化氧化;(2)CH4催化轉(zhuǎn)化;(3)催化脫羧反應(yīng),并重點(diǎn)關(guān)注貴金屬單原子摻雜團(tuán)簇獨(dú)特的催化反應(yīng)性.單原子催化劑可最大限度地利用有限的貴金屬.在化學(xué)反應(yīng)方面,單原子催化劑具有特異的反應(yīng)活性,選擇性以及穩(wěn)定性.本綜述對(duì)氣相團(tuán)簇反應(yīng)中報(bào)道的兩個(gè)重要的貴金屬單原子摻雜團(tuán)簇的催化反應(yīng)進(jìn)行了詳細(xì)介紹:(1)金原子摻雜的Au Al_3O_(3-5)~+團(tuán)簇為首次報(bào)道的可以利用分子氧催化氧化CO的團(tuán)簇單原子催化劑,我們對(duì)Au原子起催化作用的本質(zhì)原因進(jìn)行了介紹:(2)鉑原子摻雜的Pt Al_3O_(5-7)~-團(tuán)簇能利用分子氧催化氧化CO,該研究提出了"電負(fù)性階梯"效應(yīng)來(lái)解釋Pt原子催化的微觀機(jī)理,且此效應(yīng)有望對(duì)大部分貴金屬適用.此外,本綜述對(duì)CO催化氧化反應(yīng)和CH_4催化轉(zhuǎn)化反應(yīng)的研究現(xiàn)狀以及尚未解決的問(wèn)題進(jìn)行了剖析.相比CO的催化氧化反應(yīng),科學(xué)家對(duì)CH4催化轉(zhuǎn)化反應(yīng)機(jī)理的認(rèn)識(shí)還不夠深入,還需要進(jìn)一步實(shí)驗(yàn)研究,而團(tuán)簇單原子催化劑有望在此領(lǐng)域有所突破.
[Abstract]:Metal catalysts have important applications in industrial, environmental, energy and biological processes. The design of catalysts with specific activity, environmental friendliness and reaction activity at room temperature requires a full understanding of the basic steps of metal catalysts, the structure of active sites and the microscopic mechanism of catalytic reactions at the molecular level. However, because the surface structure of macroscopic catalyst is very complicated, the catalytic reaction is often interfered by solvent, pressure, metal particle agglomeration, catalyst surface defect and so on. It is still a challenge to explore the mechanism of metal catalytic reaction from the micro point of view. Therefore, the structure of the active site of metal catalyst and the micro mechanism of the reaction are not well understood. The mass spectrometry method combined with the modern quantum chemistry theory provides a powerful tool for the experimental exploration of the microscopic mechanism of chemical reactions in the gas phase. Cluster reactions can be carried out under isolated, controllable and repeatable conditions. The interference of some uncontrollable factors can be eliminated and the structure of active sites of metals and the microscopic mechanism of catalytic reactions can be recognized at the level of chemical bond and molecular structure. Gas phase metal cluster ions can be prepared by a variety of experimental methods. After reacting with reactants, they can be detected by various mass spectrometry instruments. According to the experimental results of clusters with reactive activity and modern quantum chemistry theory simulation, The basic steps and microcosmic reaction mechanism information of metal-catalyzed reaction were obtained. The obtained reaction mechanism information provided an important theoretical basis for the design of macroscopic catalysts. This review summarizes the gas phase reactions catalyzed by metal monatomic ions, metal clusters, metal oxide clusters and metal compounds, which have been detected in cluster experiments. The reactants contain a large number of inorganic and organic molecules, including the COHSP 2CH4S / C2H2S / C2H2S / C2H4 / C6H6 / CH3HCOOH- CH3COOH. In this review, the following three kinds of catalytic reactions: 1: 1 ~ (1) CO catalytic oxidation of C ~ (2 +) H _ (2) H _ (4) and ~ (3)) catalytic decarboxylation are introduced, with emphasis on the unique catalytic reactivity of noble metal monatomic doped clusters. Monatomic catalysts can maximize the use of limited precious metals. In chemical reaction, monatomic catalyst has specific activity, selectivity and stability. In this paper, the catalytic reactions of two important noble metal monoatomic doped clusters reported in the gas phase cluster reaction are introduced in detail. Cluster monatomic catalyst, We have introduced the essential reason for the catalytic action of au atoms. (2) Platinum doped Pt Al3O / 5 / 7C clusters can use molecular oxygen to catalyze the oxidation of CO.In this study, the electronegativity ladder effect is proposed to explain the microscopic mechanism of Pt atom catalysis. This effect is expected to be applicable to most precious metals. In addition, the research status and unsolved problems of CO catalytic oxidation and CH_4 catalytic conversion were analyzed. Compared with the catalytic oxidation of CO, the mechanism of catalytic conversion of CH4 is not well understood by scientists, and further experimental research is needed, and the cluster monatomic catalyst is expected to make a breakthrough in this field.
【作者單位】： 中國(guó)科學(xué)院化學(xué)研究所動(dòng)態(tài)與穩(wěn)態(tài)結(jié)構(gòu)實(shí)驗(yàn)室;華南理工大學(xué)化學(xué)與化工學(xué)院;
【基金】：supported by the National Natural Science Foundation of China(21303215,21325215,21573246) the Major Research Plan of China(No.2013CB834603) the grant from the Youth Innovation Promotion Association,Chinese Academy of Sciences(2016030)~~
【分類號(hào)】：O643.32

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