【摘要】：近年來,隨著經(jīng)濟社會的飛速發(fā)展,資源的枯竭和環(huán)境的污染已嚴重制約經(jīng)濟的進一步發(fā)展,甚至威脅到人類的生存與發(fā)展,開發(fā)新的催化劑制備方法成為解決這一問題的有力手段之一。通常的催化劑制備是在水相中進行,其不可避免會帶來水環(huán)境污染等問題。與此對應的是,當催化劑的制備在無水條件下進行,可有效避免水污染。以此為立足點,在本論文中,我們選取兩類具有代表性的催化劑構型(負載型催化劑和復合氧化物催化劑)為研究對象,詳細考察了固相法在制備高性能催化劑方面所具有的優(yōu)勢,同時結合多種物理化學表征手段,系統(tǒng)考察制備參數(shù)對催化劑的影響,深入剖析催化劑制備的中間過程,探究催化劑結構-性能間的關聯(lián)。主要研究內(nèi)容如下：1、以簡單硝酸鹽為金屬氧化物前驅(qū)體,SBA-15為載體,通過固相法制備了高含量、單分散的SBA-15孔道內(nèi)裝載的金屬氧化物(NiO, Co3O4, CeO2)納米顆粒催化劑。N2吸附和透射電鏡表明,納米顆粒填充在介孔孔道內(nèi)。而X射線衍射和透射電鏡確認了納米粒子的單分散性。進一步以鎳為研究對象,全面考察了不同氧化鎳含量、不同焙燒溫度、不同前驅(qū)體以及孔道對制備結果的影響,同時研究了孔道限域?qū)腕w物種分解及聚集長大的影響。結果表明,NiO顆粒大小隨著含量及溫度增加未發(fā)生明顯變化；前驅(qū)體種類以及是否存在介孔對制備結果影響較大,使用醋酸鎳為鎳源不能使鎳鹽進入介孔孔道,最終只能得到孔道外的大顆粒NiO；孔道的限域作用使得金屬鹽的分解和納米顆粒的急劇長大受到明顯的抑制。結合對制備中間過程的研究結果,我們推測硝酸鎳前驅(qū)體在受熱過程中形成的熔鹽的流動性是確保鎳物種進入SBA-15孔道的前提,而熔鹽的粘度性質(zhì)則保證了粒子的單分散性。最后,我們考察了鎳催化劑在氯苯加氫脫氯以及NH3分解制氫反應中的活性,發(fā)現(xiàn)相對于常規(guī)方法(浸漬法),固相法得到的催化劑具有更好的活性。這一結果顯示了固相法在污染物治理和清潔能源生產(chǎn)方面的潛在應用。2、以硝酸銅為銅鹽前驅(qū)體,SBA-15為載體,使用固相法首次將高含量(20 wt%)銅物種鍵合到SBA-15表面,而使用常規(guī)浸漬法主要得到大顆粒的晶相CuO。進一步對固相法制備樣品進行X射線衍射,H2程序升溫還原,原位紅外等表征,確認了銅物種以與SBA-15表面羥基共同縮合脫水形式鍵合到SBA-15,其存在形式為孤立的銅二聚體。另一方面,我們還對載體的影響進行了考察,結果表明載體的比表面積不是決定銅物種能夠成功鍵合的關鍵,而SBA-15的獨特孔道結構帶來的毛細吸附對銅物種的分散至關重要。3、通過固相法制備了負載型銅鈰催化劑,同時考察了其在富氫CO選擇性氧化中(CO-PROX)的性能。我們發(fā)現(xiàn),CeO2顆粒大小以及銅鈰間的相互作用顯著地影響到反應活性。由于固相法可以減小Ce02大小,同時相比于常規(guī)浸漬法,其還可以加強銅鈰間的相互作用,因此展現(xiàn)出優(yōu)異的CO-PROX活性。另外,通過比較無定形硅膠與SBA-15這兩種不同載體,發(fā)現(xiàn)無定形硅膠具有更高的活性,這可能與反應物分子的在孔道內(nèi)擴散會受到一定限制所致。4、使用固相法制備了鎳鈰復合氧化物催化劑,并考察了其在NO+CO反應中的性能。通過與常規(guī)浸漬法、共沉淀法比較,發(fā)現(xiàn)固相法在制備鎳鈰復合氧化物催化劑方面具有以下優(yōu)勢：(1)固相法可以避免活性物種的流失；(2)固相法有利于得到高比表面積催化劑,這可能與制備過程中金屬鹽分解釋放的NOx等氣體有關,其會給催化劑帶來細小孔道結構；(3)固相法制備過程有利于鎳和鈰作用的加強。這些加強作用的鎳鈰主要體現(xiàn)在高度分散在Ce02表面的NiO以及摻入Ce02晶格中的Ni2+。正因為這些結構和物種方面的性質(zhì),使得固相法制備催化劑在NO+CO反應中表現(xiàn)出優(yōu)良活性。進一步考察不同鎳鈰比,發(fā)現(xiàn)當鎳鈰摩爾比為1：9時,催化劑的NO+CO活性最佳。過多或過少的鎳都不利于催化活性的提升。
[Abstract]:In recent years, with the rapid development of the economy and society, the exhaustion of resources and the pollution of the environment have seriously restricted the further development of the economy, and even threatened the survival and development of the human, and the new preparation method of the catalyst has become one of the powerful tools to solve the problem. The usual preparation of the catalyst is carried out in the aqueous phase, which inevitably leads to problems of water environmental pollution and the like. Correspondingly, when the preparation of the catalyst is carried out under the anhydrous condition, the water pollution can be effectively avoided. In this paper, we selected two representative catalyst configurations (supported catalyst and composite oxide catalyst) as the research object, and the advantages of the solid-phase method in the preparation of high-performance catalysts were investigated in detail. At the same time, the influence of the preparation parameters on the catalyst was investigated in combination with a variety of physical and chemical characterization methods, and the intermediate process of the catalyst preparation was analyzed, and the relationship between the structure and the performance of the catalyst was investigated. The main contents of the study are as follows:1. The metal oxide (NiO, Co3O4, CeO2) nano-particle catalyst loaded in the SBA-15 channel with high content and single dispersion is prepared by the solid-phase method with the simple nitrate as the metal oxide precursor and the SBA-15 as the carrier. The N2 adsorption and transmission electron microscope show that the nano-particles are filled in the mesoporous channel. The monodispersity of the nanoparticles was confirmed by X-ray diffraction and transmission electron microscopy. The effect of different nickel oxide content, different firing temperature, different precursor and pore channel on the preparation results was further investigated with nickel as the research object, and the effect of the pore-limited region on the decomposition and aggregation of the object species was also studied. The results show that the size of NiO particles has not changed significantly with the increase of content and temperature; the type of the precursor and the existence of the mesopore have great influence on the preparation result, and the nickel acetate is used as the nickel source, so that the nickel salt can not enter the mesoporous channel, and the large-particle NiO outside the pore canal can only be obtained; The limited domain effect of the pore canal makes the decomposition of the metal salt and the rapid growth of the nano-particles to be obviously inhibited. In combination with the results of the preparation of the intermediate process, we speculate that the fluidity of the molten salt formed during the heating process of the nickel nitrate precursor is the premise of ensuring that the nickel species enters the SBA-15 pore canal, and the viscosity property of the molten salt ensures the monodispersity of the particles. In the end, we investigated the activity of the nickel catalyst in the hydrodechlorination of the chlorobenzene and the hydrogen production from the decomposition of NH3, and found that the catalyst obtained by the solid-phase method has better activity relative to the conventional method (impregnation method). the results show that the solid-phase method is a potential application for pollutant treatment and clean energy production.2, the copper nitrate is a copper salt precursor, the SBA-15 is a carrier, a high content (20 wt%) copper species is bonded to the SBA-15 surface for the first time by using a solid phase method, And the crystal phase cuo of the large particles is mainly obtained by using the conventional impregnation method. The samples were further characterized by X-ray diffraction, H2 program temperature-raising and reduction, in-situ IR, etc., and the copper species were bonded to SBA-15 in the form of isolated copper dimer in the form of co-condensation and dehydration with the hydroxyl group of SBA-15. The results show that the specific surface area of the carrier is not the key to the successful bonding of the copper species, and the capillary adsorption of the unique pore structure of the SBA-15 is very important to the dispersion of the copper species. Supported copper-based catalysts were prepared by solid-phase method, and the performance of CO-PROX in the selective oxidation of hydrogen-rich CO was also investigated. We have found that the size of the CeO2 particles and the interaction of the copper particles significantly affect the activity of the reaction. Due to the fact that the solid phase method can reduce the size of the Ce02, it is also possible to enhance the interaction between the copper particles as compared to the conventional impregnation method, thus exhibiting excellent CO-PROX activity. In addition, by compare that two different support of the amorphous silica gel and the SBA-15, it is found that the amorphous silica gel has a higher activity, which may be caused by a certain limit to the diffusion of the reactant molecules in the pore canal. The performance of its in NO + CO reaction was also investigated. Compared with the conventional impregnation method and the coprecipitation method, the solid-phase method has the advantages of: (1) the solid-phase method can avoid the loss of the active species; and (2) the solid-phase method is favorable for obtaining the high-specific surface area catalyst, This may be associated with a gas such as NOx released from the decomposition of the metal salt during the preparation process, which results in a fine pore structure for the catalyst; and (3) the solid phase preparation process is beneficial to the enhancement of the effect of nickel and sulfur. These reinforcing nickel alloys are mainly represented by NiO which is highly dispersed on the surface of Ce02 and Ni2 + incorporated in the Ce02 lattice. Due to the nature of these structures and species, the preparation of the catalyst in the solid phase process exhibits excellent activity in the NO + CO reaction. It was found that the NO + CO activity of the catalyst was the best when the molar ratio of nickel to nickel was 1:9. Too much or too little nickel is detrimental to the catalytic activity.
【學位授予單位】：南京大學
【學位級別】：博士
【學位授予年份】：2011
【分類號】：X505;O643.36

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