凹凸棒土复合材料在催化领域的应用现状

doi:10.19964/j.issn.1006-4990.2020-0557

摘要/Abstract

摘要：

凹凸棒土作为一种非金属矿物材料,储量丰富,结构特殊,具有良好的吸附性能和催化性能,常用作催化剂或催化剂载体。为了更好地了解并充分利用凹凸棒土资源,概括介绍了凹凸棒土的基本性质及包括酸改性、碱改性在内的不同改性方法对凹凸棒土自身性质的影响,主要叙述了凹凸棒土复合材料在光催化、气相催化、电催化及其他催化领域的应用现状。通过对比发现,凹凸棒土复合材料在各催化领域尤其是光催化领域应用价值较高。最后,对该复合材料在光催化治理废水污染物中所具有的优势和发展前景进行了总结和展望。

关键词: 凹凸棒土, 复合材料, 光催化, 气相催化, 电催化

Abstract:

As a non-metallic mineral material,attapulgite has abundant reserves and special structure.Due to its good adsorp-tion performance and catalytic performance,it is commonly used as catalyst or catalyst carrier.In order to better understand and make full use of attapulgite resources,the basic properties of attapulgite and the influence of different modification meth-ods including acid modification and alkali modification on the properties of attapulgite were briefly introduced.And the cur-rent application of attapulgite composite materials in the field of photocatalysis,gas phase catalysis,electrocatalysis,and other catalysis fields were mainly described.Through comparison,the attapulgite composite material was found to exhibit higher ap-plication value in catalysis fields,especially the photocatalysis field.Finally,the advantage and the further application of the attapulgite composite materials in the treatment of wastewater by photocatalysis were summarized and prospected.

Key words: attapulgite, composite materials, photocatalysis, gas phase catalysis, electrocatalysis

中图分类号:

TB332

马瑞霄,徐娟,张燕辉. 凹凸棒土复合材料在催化领域的应用现状[J]. 无机盐工业, 2021, 53(10): 22-27.

Ma Ruixiao,Xu Juan,Zhang Yanhui. Application status of attapulgite-based composite materials in field of catalysis[J]. Inorganic Chemicals Industry, 2021, 53(10): 22-27.

图/表 6

图1

表1

表2

表3

图2

图3

参考文献 40

[1]	Wang B, Sun Z M, Sun Q, et al. The preparation of bifunctional elec-trospun air filtration membranes by introducing attapulgite for the efficient capturing of ultrafine PMs and hazardous heavy metalions[J]. Environmental Pollution, 2019, 249:851-859.
[2]	成奖国. 球磨混合硅藻土/坡缕石的吸附性能研究[J]. 矿产综合利用, 2018(2):125-129.
[3]	Zhang Y H, Dai R Y, Hu S R. Study of the role of oxygen vacancies as active sites in reduced graphene oxide-modified TiO₂[J]. Physi-cal Chemistry Chemical Physics, 2017, 19(10):7307-7315.
[4]	Zhang Y H, Gao F, Fu M L. Composite of Au-Pd nanoalloys/reduced graphene oxide toward catalytic selective organic transformation to fine chemicals[J]. Chemical Physics Letters, 2018, 691:61-67.
[5]	Zhou H, Zhang Y H. Efficient thermal and photocatalysts made of Au nanoparticles on MgAl-layered double hydroxides for energy and environmental applications[J]. Physical Chemistry Chemical Physics, 2019, 21(39):21798-21805.
[6]	Huang Y X, Lin H, Zhang Y H. Synjournal of MIL-101(Fe)/SiO₂ co-mposites with improved catalytic activity for reduction of nitroaro-matic compounds[J]. Journal of Solid State Chemistry, 2020, 283.Doi: 10.1016/j.jssc.2019.121150.
[7]	田利强, 孙根行, 姜铭峰. 改性凹凸棒黏土对阳离子染料的脱色性能[J]. 印染, 2017, 43(11):16-19,32.
[8]	唐森, 吴洁, 张海江, 等. 固载表面活性剂的凹土催化剂的制备及应用[J]. 无机盐工业, 2019, 51(5):82-86.
[9]	陈雪芳, 熊莲, 王璨, 等. 酸改性对低品位凹凸棒石的白度和组成结构的影响[J]. 硅酸盐通报, 2017, 36(12):4198-4204.
[10]	韩梅香, 尹洪斌, 唐婉莹. 热改性凹土钝化底泥对水体磷的吸附特征研究[J]. 中国环境科学, 2016, 36(1):100-108.
[11]	Yang X L, Zhang P J, Li X B, et al. Effervescence-assisted β-cy-clodextrin/attapulgite composite for the in-syringe dispersive solid-phase extraction of pyrethroids in environmental water samples[J]. Talanta, 2016, 153:353-359.
[12]	韶晖, 姚鹏飞, 冷一欣, 等. 凹凸棒土的改性及其对己烷异构体的吸附性能[J]. 化学工程, 2014, 42(12):15-19.
[13]	Tan L Q, Wang X X, Tan X L, et al. Bonding properties of humicacid with attapulgite and its influence on U(Ⅵ) sorption[J]. Che-mical Geology, 2017, 464:91-100.
[14]	房百惠, 王童, 董浩, 等. 碱改性凹凸棒土对Cu²⁺吸附效果及其作用机理的研究[J]. 齐鲁工业大学学报, 2020, 34(2):19-23.
[15]	米璇, 郭睿, 王文姬. 铝改性凹凸棒土吸附剂在含氟废水中的应用[J]. 非金属矿, 2019, 42(4):86-89.
[16]	Pan C G, Liu P. Surface modification of attapulgite nanorods with nitrile butadiene rubber via thiol-ene interfacial click reaction:Grafting or crosslinking[J]. Industrial & Engineering Chemistry Research, 2018, 57(14):4949-4954.
[17]	顾韵婕, 韩粉女, 唐喆, 等. 低温选择性催化还原脱硝催化剂CeVO₄/凹凸棒土的制备和性能研究[J]. 化工新型材料, 2015, 43(3):51-53.
[18]	李亚, 佘德琴, 蒋云霞, 等. 凹土负载KF/CaO复合固体碱催化废油脂合成生物柴油[J]. 中国油脂, 2016, 41(11):66-69.
[19]	金德宽, 严群芳. TiO₂/凹土光催化剂降解活性深蓝K-R动力学[J]. 实验室研究与探索, 2011, 30(11):194-196,204.
[20]	Chen S, Huang D L, Xu P, et al. Facet-engineered surface and in-terface design of monoclinic scheelite bismuth vanadate for enhan-ced photocatalytic performance[J]. ACS Catalysis, 2020, 10(2):1024-1059.
[21]	李亚, 丁敏娟, 李蓉, 等. 黏土基二氧化钛水热制备及其光催化性能研究[J]. 无机盐工业, 2018, 50(12):75-78,82.
[22]	崔家民, 杨艳青, 靳虎芳, 等. 凹凸棒/Bi₂WO₆光催化复合材料的制备及性能[J]. 复合材料学报, 2019, 36(9):2119-2130.
[23]	甄文媛, 李青. 超临界干燥法制备TiO₂/凹凸棒复合光催化剂[J]. 化工学报, 2018, 69(5):2290-2298.
[24]	朱鹏飞, 刘梅, 张杰, 等. Fe-Ni共掺杂ZnO/凹凸棒光催化降解废水中抗生素性能研究[J]. 安全与环境学报, 2015, 15(5):230-234.
[25]	石莹莹, 邵明丽, 陈斌. Bi₂WO₆-ATP的制备及其可见光催化降解四环素的研究[J]. 非金属矿, 2018, 41(3):87-89.
[26]	Li X Z, He C L, Zuo S X, et al. Photocatalytic nitrogen fixation over fluoride/attapulgite nanocomposite:Effect of upconversion and fluo-rine vacancy[J]. Solar Energy, 2019, 191:251-262.
[27]	Xie A J, Tao Y W, Zhang W Q, et al. Synthesizing CeO₂-NiTiO₃/attapulgite and investigating the conversion rate of NO_x,sulfur re-sistance,N₂ selectivity,and stability of the catalyst through applied SCR by upper-level undergraduate students[J]. ACS Journal of Chemical Education, 2020, 97(6):1660-1665.
[28]	Zuo S X, Chen Y, Wu M D, et al. Preparation of Ag@AgBr/C₃N₄-attapulgite composite for photocatalytic desulfurization[J]. Journal of the Chinese Ceramic Society, 2017, 45(7):1024-1030.
[29]	Zhang C T, Hu X, Yu Z J, et al. Steam reforming of acetic acid for hydrogen production over attapulgite and alumina supported Ni ca-talysts:Impacts of properties of supports on catalytic behaviors[J]. International Journal of Hydrogen Energy, 2019, 44(11):5230-5244.
[30]	Wei Y X, Song M, Yu L, et al. Hydroxyl-promoter on hydrated Ni-(Mg,Si) attapulgite with high metal sintering resistance for bio-mass derived gas reforming[J]. International Journal of Hydrogen Energy, 2019, 44(36):20056-20067.
[31]	Feng P, Huang K, Xu Q L, et al. Ni supported on the CaO modified attapulgite as catalysts for hydrogen production from glycerol steam reforming[J]. International Journal of Hydrogen Energy, 2020, 45(15):8223-8233.
[32]	叶志勇. 固定床三维电极电催化氧化深度处理氨氮废水[J]. 矿产综合利用, 2014(3):55-57.
[33]	王元有, 黄星雨, 刘天晴. 凹凸棒土/石墨复合材料电极的制备及性质[J]. 无机盐工业, 2015, 47(1):72-74.
[34]	蒋青松, 陈若婷, 周禹含, 等. CoSe-凹土对电极设计构筑及其电催化性能研究[J]. 非金属矿, 2017, 40(5):1-4.
[35]	张盛, 蒋亿, 纪媛媛, 等. 凹凸棒石/g-C₃N₄复合材料的制备及其电催化析氧性能研究[J]. 无机材料学报, 2019, 34(8):803-810.
[36]	刘阳钰, 胡志波, 郑水林. 煅烧温度对NaCl/凹凸棒土复合材料调湿性能的影响[J]. 非金属矿, 2015, 38(6):9-10,41.
[37]	Zhang Y Y, Wei X Y, Lv J H, et al. Catalytic hydroconversion of a high-temperature coal tar over two attapulgite powder-supported nickel catalysts[J]. Energy & Fuels, 2020, 34(2):1288-1296.
[38]	王延涛, 梁财, 周群, 等. 凹凸棒石镍基催化剂对污泥气化焦油催化裂解的特性分析[J]. 化工进展, 2018, 37(10):3895-3902.
[39]	Yuan B, Yin X Q, Liu X Q, et al. Enhanced hydrothermal stability and catalytic performance of HKUST-1 by incorporating carboxyl-functionalized attapulgite[J]. ACS Applied Materials & Interfaces, 2016, 8(25):16457-16464.
[40]	王鑫, 吴诗敏, 万弋, 等. 多孔结构凹土制备及甲醛吸附性能研究[J]. 非金属矿, 2019, 42(1):104-106.

改性方法	改性机理	主要改性结果
酸改性^[9,13]	去除大颗粒物质及MgO、Al₂O₃等氧化物和碳酸盐类杂质;打断和分散凹土内部密集的晶束;H⁺置换出晶体间的K⁺、Na⁺和Mg²⁺等离子	孔隙率增大,活性位点增多;改变表面带电性
碱改性^[14]	腐蚀凹土中Si—O—Si（M）键;OH^-与部分替换出的阳离子结合生成沉淀;置换出凹土内部存在的金属阳离子（如Na⁺置换Al³⁺等）	增大孔容体积和比表面积;提高吸附能力;增强表面负电性
盐改性^[15]	与酸改性相似,半径小的离子置换出凹土层间半径较大的离子	疏通孔道,增大比表面积;增加活性位点,提高吸附性
热改性^[7,10]	在不同温度下蒸发凹土内部不同的水分	增大比表面积;增强吸附能力
有机改性^[11,16]	凹土表面带负电荷,大多使用阳离子表面活性剂改性; 在凹土表面接枝特定官能团（如接枝含氨基的大分子等）	提高吸附能力和选择性;增强或改变表面的带电性;增强疏水性

材料	改性或复合前比表面积/（m²·g^-1）	改性或复合后比表面积/（m²·g^-1）
350 ℃改性凹土^[7]	97.48	116.78
β-环糊精改性凹土^[12]	81.10	88.20
铝盐改性凹土^[15]	13.61	121.99
CeVO₄-ATP复合材料^[17]	139.437	217.571

制备方法	优点	缺点
水热法^[17]	设备要求低,条件可控,制作成本低	能耗大,一般耗时较长
浸渍法^[18]	操作简便,要求低	稳定性有待提高
溶胶-凝胶法^[19]	合成温度低,产品尺寸小	反应时间较长,有时涉及有害物质

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会