類固體酸催化劑研究進(jìn)展

廖 洋, 趙仕林

(1. 四川師范大學(xué) 化學(xué)與材料科學(xué)學(xué)院, 四川 成都 610066; 2. 四川省高校農(nóng)田生態(tài)服務(wù)能力建設(shè)工程中心, 四川 成都 610066)

廖 洋1,2, 趙仕林1,2

(1. 四川師范大學(xué) 化學(xué)與材料科學(xué)學(xué)院, 四川 成都 610066; 2. 四川省高校農(nóng)田生態(tài)服務(wù)能力建設(shè)工程中心, 四川 成都 610066)

固體酸； 制備方法； 改性； 催化性能

1.5模板法

綜上所述，從提高比表面積的凝膠-溶膠法、到制備粒度較小甚至納米級(jí)別的水熱合成法和低溫陳化法，再到構(gòu)建介孔結(jié)構(gòu)的模板制備法，這些制備方法各有其優(yōu)缺點(diǎn)，總的來說為了提高固體酸的比表面積，增加活性點(diǎn)位，提高其催化活性.同時(shí)，不同制備方法中具體的合成條件也會(huì)影響其催化劑最終生成的結(jié)構(gòu)，會(huì)對(duì)酸強(qiáng)度的大小和酸活性點(diǎn)位的分布產(chǎn)生影響，進(jìn)而影響到催化劑的催化活性.

2.1引入稀土元素少量稀土元素的加入可以改變催化劑表面的化學(xué)狀態(tài)，有助于形成穩(wěn)定晶型結(jié)構(gòu)，提高催化劑載體的機(jī)械強(qiáng)度和熱穩(wěn)定性，改善催化劑的活性和壽命.以稀土摻二氧化鈦[53]為例，少量的稀土摻雜可以造成金屬表面晶體缺陷，使得二氧化鈦金屬表面產(chǎn)生更多催化性能的空穴.但過量時(shí)，二氧化鈦的催化能力下降,因?yàn)閾诫s的量對(duì)金屬表面的空間電荷層厚度起到了相反的作用.只有當(dāng)空間電荷層厚度近似入射光進(jìn)入固體的透入深度時(shí)，金屬吸收光子產(chǎn)生的電子-空穴才能分離.

3 結(jié)論

[4] 許越. 催化劑設(shè)計(jì)與制備工藝[M]. 北京:化學(xué)工業(yè)出版社,2003:121.

[14] VISHWANATHAN V, BALAKRISHNA G, RAJESH B, et al. Alkylation of catechol with methanol to give guaiacol over sulphate-modified zirconia solid acid catalysts:the influence of structural modification of zirconia on catalytic performance[J]. Catalysis Communications,2008,9(14):2422-2427.

[16] FURUTA S, MATSUHASHI H, ARATA K. Biodiesel fuel production with solid superacid catalysis in fixed bed reactor under atmospheric pressure[J]. Catalysis Communications,2004,5(12):721-723.

[21] DAVID A W, EDMOND I K. One-step synthesis and characterization of zirconia-sulfate aerogels as solid superacids[J]. Journal of Catalysis,1994,150(1):18-33.

[22] LOPEZ T, BOSCH P, TZOMPANTZI F, et al. Effect of sulfation methods on TiO2-SiO2sol-gel catalyst acidity[J]. Applied Catalysis:General,2000,A197(1):107-117.

[23] MA H, LI J B, LIU W W, et al. Hydrothermal preparation and characterization of novel corncob-derived solid acid catalysis[J]. Journal of Agricultural and Food Chemistry,2014,62(23):5345-5353.

[36] HALL S R, BOLGER H, MANN S. Morphosynthesis of complex inorganic forms using pollen grain templates[J]. Chemical Communications,2003,35(22):2784-2785.

[37] HALL S R, SWINERD V M, NEWBY F N, et al. Fabrication of porous titania (brookite) microparticles with complex morphology by sol-gel replication of pollen grains[J]. Chemistry of Materials,2006,18(3):598-600.

[39] CIESLA U, SCHACHT S, STUCK G D, et al. Formation of a porous zirconium oxo phosphate with a high surface area by a surfactant-assisted synthesis[J]. Angewandte Chemie International Edition,1996,35(5):541-543.

[43] LIAO X P, ZHANG M N, SHI B. Collagen-fiber-immobilized tannins and their adsorption of Au(III)[J]. Industrial & Engineering Chemistry Research,2004,43(9):2222-2227.

[44] CAI L, LIAO X P, SHI B. Using collagen fiber as a template to synthesize TiO2and Fex /TiO2nanofibers and their catalytic behaviors on the visible light-assisted degradation of orange II[J]. Industrial & Engineering Chemistry Research,2010,49(7):3194-3199.

[45] 蔡莉. 膠原纖維為模板TiO2、Lax/TiO2納米纖維的制備、表征及光催化活性研究[J].功能材料,2014,45(1):1015-1019.

[47] 張志芳. 負(fù)載型固體酸的制備及催化環(huán)酮Baeyer-Villiger氧化反應(yīng)研究[D]. 蘭州:西北師范大學(xué),2012:33-38,69-71.

[48] FRAENKEL D. Structure of sulfated metal oxides and its correlation with catalytic activity[J]. Industrial & Engineering Chemistry Research,1997,36(1):52-59.

[55] 杜強(qiáng). 摻雜稀土固體酸的制備及催化性能[D]. 成都:四川師范大學(xué),2012:61-62.

[58] LANGE F C, CHEUNG T K, GATES B C. Manganese, iron, cobalt, nickel, and zinc as promoters of sulfated zirconia forn-butane isomerization[J]. Catalysis Letters,1996,41(1/2):95-99.

[63] VIEIRA S S, MAGRIOTIS Z M, RIBEIRO M F, et al. Use of HZSM-5 modified with citric acid as acid heterogeneous catalyst for biodiesel production via esterification of oleic acid[J]. Microporous and Mesoporous Materials,2015,201:160-168.

[64] QIN Q D, XU Y. Enhanced nitrobenzene adsorption in aqueous solution by surface silylated MCM-41[J]. Microporous and Mesoporous Materials,2016,232:143-150.

LIAO Yang1,2, ZHAO Shilin1,2

(1.CollegeofChemistryandMaterialsScience,SichuanNormalUniversity,Chengdu610066,Sichuan; 2.EngineeringCenterfortheDevelopmentofFarmlandEcosystemServiceFunction,SichuanNormalUniversity,Chengdu610066,Sichuan)

solid acid; preparation; modification; catalytic properties

2016-07-08

國家自然科學(xué)基金(21406147和41641010)、四川省科技支撐項(xiàng)目(2016NZ0053)和成都市科技項(xiàng)目(2014-HM01-00204-SF)

廖 洋(1979—),副教授,主要從事環(huán)境材料與污染治理的研究,E-mail:liaoyang_sicnu@163.com

Q949O643.3

A

1001-8395(2017)05-0577-08

10.3969/j.issn.1001-8395.2017.05.002

(編輯 周 俊)