Progress on bio-templated synthesis of metal oxides and their catalytic applications

doi:10.16085/j.issn.1000-6613.2018-1378

Abstract

Abstract:

In natural environment, multilevel and multidimensional, and multi-scale natural hard template structure from long-term evolution and some "soft" natural biological molecules with multi-level, multi-dimensional structure provide a new venue for hierarchically structural design and preparation of nanomaterials. Metal oxides are usually employed as an important component of the catalyst. Therefore, their preparation and catalytic applications have received much attention. Bio-templated synthesis provides a simple, green and efficient synthetic route to the metal oxide. This review summarized the research progress in recent ten years from the aspects of preparation methods based on bio-templates, the roles of biological templates in the oxide preparation process and in catalytic application of metal oxides. The preparation method based on hard template is simple and efficient and can perfectly duplicate metal oxide materials with similar structures, while the soft template can flexibly regulate the size and dispersibility of metal oxide particles. Based on the bio-templated synthesis, the formation of metal oxide often experiences multi-steps of "adsorption-nucleation and growth-assembly", where bio-template plays important roles in the surface adsorption, confinement, orientation, etc. For catalytic applications of the metal oxide, bio-templated synthesis offers the advantage to enable the elemental self-doping of metal oxide, effectively improve mass transfer, and special surface structure of metal oxide endows the resulting catalyst with excellent catalytic performance.

Key words: biotemplate, metal oxide, nanomaterial, catalyst

摘要：

自然环境中长期进化形成的多层次、多维和多尺度天然硬模板结构和一些具有多层次多维结构的天然“软”生物分子可为多级结构纳米材料的设计与制备提供了新的思路。金属氧化物通常作为催化剂的重要组成部分，其制备与催化应用得到广泛关注，生物模板法为金属氧化物的制备提供了一条简单、绿色、有效的合成路线。本文从基于生物模板的制备方法、生物模板在氧化物制备过程中的作用和生物模板在金属氧化物催化应用时的作用方面总结近十年来的研究进展。基于硬模板的制备方法简单高效，可完美地复制结构类似的金属氧化物材料，而软模板能够灵活地调控金属氧化物颗粒的尺寸和分散性。基于生物模板制备金属氧化物的过程往往经历“吸附-成核-生长-组装”多步骤，生物模板起着表面吸附、空间限域、导向等重要作用。就所得金属氧化物的催化应用而言，生物模板法的优势在于能够实现氧化物材料元素的自掺杂、有效改善传质以及特殊的表面结构赋予催化剂优异的催化性能。

关键词: 生物模板, 金属氧化物, 纳米材料, 催化剂

CLC Number:

TQ13

Xia JIANG, Wen LI, Yunlong GUO, Lu WANG, Qun LI, Qingbiao LI. Progress on bio-templated synthesis of metal oxides and their catalytic applications[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 485-494.

姜霞, 李雯, 郭云龙, 王璐, 李群, 李清彪. 生物模板法制备金属氧化物及其催化应用研究进展[J]. 化工进展, 2019, 38(01): 485-494.

Figures/Tables 5

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硬模板	金属氧化物	制备方法	应用
向日葵花粉^[6]	CoFe₂O₄	LBL+SSG^②(WCM)	—^①
油菜花粉^[7]	PGs@(Ti-Zr)O₄	WCM	蛋白质检测
百合花粉^[8]	TiO _x /C或SiO _x /C	WCM	光催化降解活性艳红X-3B染料
A.trifida花粉^[9]	TiO₂	WCM	光催化降解罗丹明B染料
油菜花粉^[10]	ZrO₂	WCM	吸附刚果红染料
松花粉^[11]	MgFe₂O₄/γ-Fe₂O₃	WCM	刚果红染料和二甲胺四环素药物的废水处理
P. pterocarpum花粉^[12]	SnO₂	WCM	—^①
蒲公英花粉^[13]	CoFe₂O₄	WCM	盐酸阿霉素药物释放
荷花花粉^[14]	MnO/C	WCM	锂离子电池
荷花花粉^[15]	WO₃	WCM	NO 传感器
棕榈树花粉^[16]	ZnO	WCM	—^①
向日葵花粉^[17]	赤铁矿/α-Fe₂O₃/Fe₃O₄	LBL+SSG^②(WCM)	—^①
荷花花粉^[18]	NiO	WCM	NO₂传感器
松树花粉^[19]	ZnAl-LDH/ZnCo₂O₄	WCM	吸附刚果红并光催化降解
油菜花粉^[20]	TiO₂	WCM	1,3-丁二烯加氢
向日葵花粉^[21]	ZrO₂	WCM	储氢
荷花花粉^[22]	CeO₂	WCM	光催化降解亚甲基蓝
油菜花粉^[23]	SnO₂	SSG^②(WCM)	气体传感器
油菜花粉^[24]	α-Fe₂O₃/C	WCM	气体传感器
向日葵花粉^[25]	Fe₃O₄	LBL+SSG^②(WCM)	—^①
花/树的花粉^[26]	CaCO₃/CaHPO₄	WCM	布洛芬药物释放
花粉^[27]	SO₄ ^2?/M1 _x O _y -M2 _x O _y （M为Zr，Mo, Ti, Wo）	WCM	氯苯的硝化反应
蒲公英花粉^[28]	TiO₂（板钛矿）	SSG^②(WCM)	光催化降解甲基蓝染料
油菜花粉^[29,30]	Cu/TiO₂	SSG^②(WCM)	光催化降解氯四环素
蝴蝶翅膀^[31]	SiO₂	CVD	以获得光子结构和光催化为主
	Al₂O₃/ TiO₂	ALD
	Y₂O₃, TiO₂/ SiO₂, ZnO, ZrO₂/ TiO₂/ SnO₂/ Fe₃O₄/ WO₃/ Bi₂WO₆, BiVO₄	WCM
芭蕉叶^[32]	TiO₂	WCM	光催化降解亚甲基蓝染料
甘蔗叶^[33]	TiO₂	WCM	光催化降解罗丹明6G
枫树叶^[34]	CeO₂	WCM	染料废水净化
芳樟叶^[35]	MgO	WCM	除菌
香樟叶^[36]	N-ZnO	WCM	光催化降解亚甲基蓝
A.vitifoliaBuch.树叶^[37]	Pt/N-doped TiO₂	SSG^②(WCM)	光催化产氢

硬模板	金属氧化物	制备方法	应用
向日葵花粉^[6]	CoFe₂O₄	LBL+SSG^②(WCM)	—^①
油菜花粉^[7]	PGs@(Ti-Zr)O₄	WCM	蛋白质检测
百合花粉^[8]	TiO _x /C或SiO _x /C	WCM	光催化降解活性艳红X-3B染料
A.trifida花粉^[9]	TiO₂	WCM	光催化降解罗丹明B染料
油菜花粉^[10]	ZrO₂	WCM	吸附刚果红染料
松花粉^[11]	MgFe₂O₄/γ-Fe₂O₃	WCM	刚果红染料和二甲胺四环素药物的废水处理
P. pterocarpum花粉^[12]	SnO₂	WCM	—^①
蒲公英花粉^[13]	CoFe₂O₄	WCM	盐酸阿霉素药物释放
荷花花粉^[14]	MnO/C	WCM	锂离子电池
荷花花粉^[15]	WO₃	WCM	NO 传感器
棕榈树花粉^[16]	ZnO	WCM	—^①
向日葵花粉^[17]	赤铁矿/α-Fe₂O₃/Fe₃O₄	LBL+SSG^②(WCM)	—^①
荷花花粉^[18]	NiO	WCM	NO₂传感器
松树花粉^[19]	ZnAl-LDH/ZnCo₂O₄	WCM	吸附刚果红并光催化降解
油菜花粉^[20]	TiO₂	WCM	1,3-丁二烯加氢
向日葵花粉^[21]	ZrO₂	WCM	储氢
荷花花粉^[22]	CeO₂	WCM	光催化降解亚甲基蓝
油菜花粉^[23]	SnO₂	SSG^②(WCM)	气体传感器
油菜花粉^[24]	α-Fe₂O₃/C	WCM	气体传感器
向日葵花粉^[25]	Fe₃O₄	LBL+SSG^②(WCM)	—^①
花/树的花粉^[26]	CaCO₃/CaHPO₄	WCM	布洛芬药物释放
花粉^[27]	SO₄ ^2?/M1 _x O _y -M2 _x O _y （M为Zr，Mo, Ti, Wo）	WCM	氯苯的硝化反应
蒲公英花粉^[28]	TiO₂（板钛矿）	SSG^②(WCM)	光催化降解甲基蓝染料
油菜花粉^[29,30]	Cu/TiO₂	SSG^②(WCM)	光催化降解氯四环素
蝴蝶翅膀^[31]	SiO₂	CVD	以获得光子结构和光催化为主
	Al₂O₃/ TiO₂	ALD
	Y₂O₃, TiO₂/ SiO₂, ZnO, ZrO₂/ TiO₂/ SnO₂/ Fe₃O₄/ WO₃/ Bi₂WO₆, BiVO₄	WCM
芭蕉叶^[32]	TiO₂	WCM	光催化降解亚甲基蓝染料
甘蔗叶^[33]	TiO₂	WCM	光催化降解罗丹明6G
枫树叶^[34]	CeO₂	WCM	染料废水净化
芳樟叶^[35]	MgO	WCM	除菌
香樟叶^[36]	N-ZnO	WCM	光催化降解亚甲基蓝
A.vitifoliaBuch.树叶^[37]	Pt/N-doped TiO₂	SSG^②(WCM)	光催化产氢

软模板	材料	结构特点	应用
细菌纤维素^[40]	ZnO	花朵状纳米颗粒	抗菌剂
纸浆^[41]	TiO₂	纤维状，大孔	光降解罗丹明B
淀粉^[42,43]	ZnO	多个小球沉积形成“甜甜圈”状等	光催化降解苯酚
酵母细胞^[44]	TiO₂	椭圆形多级有序介孔结构	光降解COD
笼型去铁蛋白^[45]	Co₃O₄	小尺寸、窄粒径分布颗粒（粒径5nm±0.7nm）	—^①
无害利斯特菌铁蛋白^[46]	Co₃O₄	小尺寸纳米颗粒（平均粒径5nm）	—^①
Mms6蛋白^[47]	Fe₃O₄	球状纳米颗粒	—^①
氨基酸^{[48,49,50,51]}	TiO₂	10～15nm立方块, 大孔径纳米棒，花球状纳米颗粒	光降解亚甲基蓝、布洛芬、萘酚蓝黑、甲基橙
天冬氨酸^[52]	TiO₂	介孔纳米球	葡萄糖脱水制糠醛
氨基酸^[53,54]	TiO₂	介孔纳米球	Li离子、Na离子电池
甘氨酸^[55]	TiO₂	介孔空心纳米球	光致发光

软模板	材料	结构特点	应用
细菌纤维素^[40]	ZnO	花朵状纳米颗粒	抗菌剂
纸浆^[41]	TiO₂	纤维状，大孔	光降解罗丹明B
淀粉^[42,43]	ZnO	多个小球沉积形成“甜甜圈”状等	光催化降解苯酚
酵母细胞^[44]	TiO₂	椭圆形多级有序介孔结构	光降解COD
笼型去铁蛋白^[45]	Co₃O₄	小尺寸、窄粒径分布颗粒（粒径5nm±0.7nm）	—^①
无害利斯特菌铁蛋白^[46]	Co₃O₄	小尺寸纳米颗粒（平均粒径5nm）	—^①
Mms6蛋白^[47]	Fe₃O₄	球状纳米颗粒	—^①
氨基酸^{[48,49,50,51]}	TiO₂	10～15nm立方块, 大孔径纳米棒，花球状纳米颗粒	光降解亚甲基蓝、布洛芬、萘酚蓝黑、甲基橙
天冬氨酸^[52]	TiO₂	介孔纳米球	葡萄糖脱水制糠醛
氨基酸^[53,54]	TiO₂	介孔纳米球	Li离子、Na离子电池
甘氨酸^[55]	TiO₂	介孔空心纳米球	光致发光

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