【摘要】：隨著化石燃料的減少和能源危機(jī)的加重,開(kāi)發(fā)利用可再生的新能源迫在眉睫.生物質(zhì)作為一種重要的可再生資源,是現(xiàn)代化學(xué)工業(yè)中的能源和有機(jī)碳的重要潛在替代物,將其轉(zhuǎn)化為高附加值化學(xué)品具有巨大的開(kāi)發(fā)潛力和實(shí)際應(yīng)用價(jià)值.因此,對(duì)于生物質(zhì)資源的高效轉(zhuǎn)化及綜合利用越來(lái)越受到人們的廣泛關(guān)注,而催化化學(xué)轉(zhuǎn)化是當(dāng)前實(shí)現(xiàn)生物質(zhì)升值利用的重要途徑之一.近年來(lái),磷酸鋯逐漸發(fā)展成為一種新型的過(guò)渡金屬磷酸鹽多功能材料,在離子交換,吸附,質(zhì)子傳導(dǎo),光化學(xué),材料化學(xué),催化等領(lǐng)域具有廣泛的應(yīng)用.根據(jù)我們和其他課題組的研究基礎(chǔ),本文簡(jiǎn)要總結(jié)了無(wú)定形、介孔和結(jié)晶型磷酸鋯(α、γ、τ)特別是α-磷酸鋯材料的制備方法,結(jié)構(gòu)和催化性能.在其結(jié)構(gòu)中,不同的磷氧基團(tuán)和水分子,鋯氧八面體和磷氧四面體通過(guò)氧橋相互連接在一起.在特定的制備條件下,可以得到無(wú)定形磷酸鋯、層狀結(jié)構(gòu)的α/γ-磷酸鋯或者三維結(jié)構(gòu)的τ-磷酸鋯.磷酸鋯材料具有極高的熱穩(wěn)定性,優(yōu)異的耐水能力,且在極性介質(zhì)(包括水相)中仍然能夠顯示出中強(qiáng)酸性,不僅具有布朗斯特酸性和路易斯酸性,而且通過(guò)控制磷和鋯的比例可以調(diào)節(jié)兩種酸的濃度.本文重點(diǎn)介紹了磷酸鋯催化劑在生物質(zhì)平臺(tái)分子轉(zhuǎn)化(如催化脫水,加氫/氫解,氧化和酯化等)反應(yīng)中的最新研究進(jìn)展,特別指出,磷酸鋯表現(xiàn)出的高熱穩(wěn)定性,耐水性和中強(qiáng)酸性使其成為具有高活性、高穩(wěn)定性的多相催化劑.已有研究表明,磷酸鋯既可以直接作為固體酸催化劑,也可以將其它金屬及其氧化物等活性組分負(fù)載于酸性磷酸鋯上,可構(gòu)建包含酸中心、金屬中心的多功能催化劑,實(shí)現(xiàn)酸催化、加氫、氧化等多步反應(yīng),從而應(yīng)用于由生物質(zhì)平臺(tái)分子制取燃料或者精細(xì)化學(xué)品催化轉(zhuǎn)化過(guò)程.總之,磷酸鋯用于生物質(zhì)轉(zhuǎn)化已經(jīng)取得了一些重要的進(jìn)展,也是目前該領(lǐng)域的研究熱點(diǎn)之一.雖然已有很多磷酸鋯催化劑的研究工作,但是在該領(lǐng)域仍然需要更加深入和廣泛的研究.在了解催化反應(yīng)機(jī)理的基礎(chǔ)上,更加精確設(shè)計(jì)、改良催化劑的結(jié)構(gòu),高效應(yīng)用在生物質(zhì)轉(zhuǎn)化以及其他催化反應(yīng)中.
[Abstract]:With the decrease of fossil fuels and the aggravation of energy crisis, the development and utilization of renewable new energy is imminent. Biomass, as an important renewable resource, is an important potential substitute for energy and organic carbon in modern chemical industry. It has great development potential and practical application value to convert biomass into high value-added chemicals. Therefore, more and more attention has been paid to the efficient conversion and comprehensive utilization of biomass resources, and catalytic chemical conversion is one of the important ways to realize biomass utilization appreciation. In recent years, zirconium phosphate has gradually developed into a new transition metal phosphate multifunctional material, which has been widely used in the fields of ion exchange, adsorption, proton conduction, photochemistry, material chemistry, catalysis and so on. According to the research basis of us and other research groups, the preparation methods, structures and catalytic properties of amorphous, mesoporous and crystallized zirconium phosphate (偽, 緯, 蟿), especially 偽 -zirconium phosphate materials, are briefly summarized in this paper. In its structure, different phosphoric groups and water molecules, zirconium oxide octahedron and phosphoric oxide tetrahedron are connected by oxygen bridge. Under specific preparation conditions, amorphous zirconium phosphate, layered 偽 / 緯 -zirconium phosphate or three-dimensional 蟿 -zirconium phosphate can be obtained. Zirconium phosphate has excellent thermal stability, excellent water resistance, and can still show moderate and strong acidity in polar media (including aqueous phase), not only Brownst acid and Lewis acid, The concentration of the two acids can be adjusted by controlling the ratio of phosphorus and zirconium. In this paper, the latest research progress of zirconium phosphate catalyst in biomass platform molecular conversion (such as catalytic dehydration, hydrogenation / hydrogenolysis, oxidation and esterification) is reviewed, especially the high thermal stability of zirconium phosphate. Water resistance and moderate acidity make it a highly active and stable heterogeneous catalyst. It has been shown that zirconium phosphate can not only be used as solid acid catalyst, but also can be loaded on acid zirconium phosphate with other active components, such as other metals and their oxides. Multi-step reactions such as acid catalysis, hydrogenation and oxidation are realized, which can be applied to the catalytic conversion process from biomass platform molecules to fuel or fine chemicals. In a word, zirconium phosphate has made some important progress in biomass conversion and is one of the research hotspots in this field. Although there have been many researches on zirconium phosphate catalysts, there is still a need for more in-depth and extensive research in this field. On the basis of understanding the mechanism of catalytic reaction, the structure of catalyst is designed more accurately, and the catalyst structure is improved, which can be used in biomass conversion and other catalytic reactions.
【作者單位】： 華東理工大學(xué)化學(xué)與分子工程學(xué)院工業(yè)催化研究所結(jié)構(gòu)可控先進(jìn)功能材料及其制備教育部重點(diǎn)實(shí)驗(yàn)室;
【基金】：support from the National Natural Science Foundation of China (21373082, 21773061) the Innovation Program of Shanghai Municipal Education Commission (15ZZ031) the Fundamental Research Funds for the Central Universities~~
【分類號(hào)】：O643.36;TK6

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本文編號(hào)：2398532