The construction of biomimetic materials and their research progress in the field of aquatic environmental chemistry

doi:10.11949/0438-1157.20221204

Abstract

Abstract:

Inspired by the biomorphic structures or chemical properties of biological molecules, many biomimetic materials are designed and attract considerable attention in the field of aquatic environmental chemistry. In this review, the research progress of biomimetic materials in that field is systematically summarized. Biomimetic materials can be designed by molecular bionics or biomorphic design. Molecular bionic approaches include re-construction or immobilization of the natural material, mimicking the active sites of biological molecules, and mimicking the catalytic environments of natural materials. These biomimetic materials have been applied in the studies of oxidative or reductive removal of contaminants from water and their detection. Its unique structure, mechanism of action and excellent performance make it have strong potential for practical application. The correlation between its microstructure and performance and the controllable synthesis method of the optimized structure are the key issues to be paid attention to in the follow-up research. Finally, the challenges and future development directions of biomimetic materials research in the field of water environment chemistry are discussed.

Key words: biomimetic material, catalyst, aquatic environment, oxidation, reduction, detection method

摘要：

仿生材料是模仿生物形貌或分子结构并具有相似功能的合成材料，在水环境化学领域的研究中被广泛关注。综述了仿生材料在该领域的研究现状。首先，总结了仿生材料的构建方法，包括生物活性单元负载或重构、活性中心结构仿生、催化环境仿生和形貌仿生。其次，梳理了仿生材料在水中污染物的氧化去除、还原去除以及检测方面的研究进展。总体而言，其独特的结构、作用机制与优异效能使其具有较强的实际应用潜力，其微观结构与效能的相关关系及最优化结构的可控合成方法是后续研究要关注的关键问题。最后，论述了水环境化学领域中仿生材料研究所面临的挑战和未来的发展方向。

关键词: 仿生材料, 催化剂, 水环境, 氧化, 还原, 检测方法

CLC Number:

X 13

Tanjie ZHA, Han YANG, Hejie QIN, Xiaohong GUAN. The construction of biomimetic materials and their research progress in the field of aquatic environmental chemistry[J]. CIESC Journal, 2023, 74(2): 585-598.

查坦捷, 杨涵, 秦荷杰, 关小红. 仿生材料的构建及其在水环境化学领域中的研究进展[J]. 化工学报, 2023, 74(2): 585-598.

Figures/Tables 7

Fig.1 The development path of biomimetic materials

Fig.2 The construction approaches and applications of biomimetic materials in the field of aquatic environmental chemistry

Fig.3 The immobilization or re-construction of natural active units in synthetized materials[16]

Table 1 The performance of bioactive molecule-loaded materials for the oxidative removal of contaminants

仿生材料	目标污染物	反应体系	反应条件	去除率（时间）	一级反应速率常数	活性氧化剂	文献
磺酸酞菁铁负载于中孔分子筛	0.1 mmol/L 孔雀绿	材料+H₂O₂+可见光	光照：500 W卤灯，可见光；T=50℃；pH₀=6.0； [材料]=200 mg/L，[H₂O₂]=6.0 mmol/L	污染物：100%（1200 min） TOC：72%（1200 min）	0.00387 min^-1	HO^•	[39]
四羧基酞菁铁（3.6%（质量））负载于大孔 SiO₂	10 μmol/L 罗丹明B	材料+O₂+可见光	光照：150 W，λ≥400 nm；[材料]=1 g/L	97.4%（60 min）	0.06 min^-1	—	[40]
酞菁铁（3.8 mg Fe/g）负载于改性聚丙烯腈纤维	0.02 mmol/L 罗丹明B	材料+H₂O₂；材料+ H₂O₂+可见光	光照：9.11 mW/cm²，λ>420 nm；T=(25±1)℃； pH₀=6.0；[材料]=4 g/L，[H₂O₂]=5 mmol/L	83%（60 min） 99%（60 min）	—	Fe(Ⅳ)O、HO^•	[48]
酞菁铁负载于改性聚丙烯腈纤维	100 mg/L盐酸四环素	材料+PMS	T=298 K；pH₀=4.0；[材料]=0.5 g/L， [PMS]=2.0 mmol/L	污染物：83%（280 min） TOC：30%（280 min）	0.00035 min^-1	SO $4 • -$ 、HO^•	[4]
酞菁铁（1.47 mg Fe/g）负载于聚苯乙烯	100 mg/L盐酸土霉素	材料+ H₂O₂	T=308 K；pH₀=4.0；[材料]=0.5 g/L， [H₂O₂]=60 mmol/L	90%（500 min）	—	HO^•	[35]
酞菁铁（0.16 mmol/g）负载于改性多壁碳纳米管	0.05 mmol/L 四氯苯酚	材料+ H₂O₂	T=50℃；pH₀=7；[材料]=0.1 g/L，[H₂O₂]=5 mmol/L	100%（90 min）	0.06293 min^-1	HO^•、HOO^•	[49]
三硝基酞菁铁（2.92 mg Fe/g）负载于活性碳纤维	0.05 mmol/L磺胺甲唑	材料+ H₂O₂	T=50℃；[材料]=0.1 g/L；[H₂O₂]=20 mmol/L	99%（90 min）	—	HO^•、Fe(Ⅳ)O、HOO^•	[37]
聚酞菁铁负载于g-C₃N₄	25 μmol/L卡马西平	材料+PMS+光	光照：模拟太阳光；pH₀=7；[材料]=0.1 g/L， [PMS]=0.3 mmol/L	100%（15 min）	—	¹O₂、SO $4 • -$ 、HO^•、O $2 • -$	[43]
酞菁铁负载于TiO₂	10 mg/L甲基橙	材料+H₂O₂+可见光	光照：150 W，28 mW/cm²，λ>400 nm；T=50℃； pH₀=7；[材料]=0.5 g/L	94%（180 min）	—	HO^•	[42]
酞菁铁（0.52%（质量）Fe）负载于海绵	2 mg/L双酚A	材料+H₂O₂+紫外光	光照：紫外光，λ>150 nm；pH₀=2；[材料]=0.04 g， [H₂O₂]=0.32 mol/L	100%（20 min）	0.0918 min^-1 （20 mg/L双酚A）	HO^•	[45]
酞菁铁负载于钴尖晶石	10 mg/L罗丹明B	材料+ H₂O₂	T=25℃；[材料]=0.50 g/L，[H₂O₂]=50 mmol/L	90%（120 min）	0.02167 min^-1	O $2 • -$ 、HO^•	[41]
酞菁钴（16.5%（质量））负载于改性多壁碳纳米管	0.05 mmol/L 酸性红	材料+H₂O₂	T=50℃；pH₀=10；[材料] =0.1 g/L， [H₂O₂] =0.01 mol/L	>98%（60 min）	—	Co(Ⅳ)O	[50]
酞菁钴（14.9 μmol/g）负载于纤维素	0.05 mmol/L 酸性红	材料+ H₂O₂ 材料+PMS	T=50℃；pH₀=6.7；[材料]=2.0 g/L， [PMS]=1.0 mmol/L，[H₂O₂]=1.0 mmol/L	5%（35 min，H₂O₂体系）；100%（35 min，PMS体系）	0.0003 min^-1（H₂O₂体系）；0.0688 min^-1（PMS体系）	PMS体系：SO $4 • -$ 、HO^•；PMS+ $H C O 3 -$ 体系： Co(Ⅳ)O	[46]
酞菁钴负载于改性分子筛	5 mg/L普兰洛尔	材料+PMS	T=25℃；pH₀=5.7±0.2；[材料]=0.1 g/L， [PMS]=0.2 g/L	93.6%（30 min）	0.0920 min^-1	¹O₂、SO $4 • -$ 、HO^•	[51]
磺酸基酞菁钴（2.24% （质量））负载于TiO₂	40 mg/L 2,4- 二氯酚	材料+ H₂O₂+紫外光	光照：400 W，紫外光；pH₀=5；[材料]=0.2 g/L，[H₂O₂]=0.03 mol/L	94%（150 min）	—	$O 2 • -$ 、HO^•	[52]

Table 1 The performance of bioactive molecule-loaded materials for the oxidative removal of contaminants

仿生材料	目标污染物	反应体系	反应条件	去除率（时间）	一级反应速率常数	活性氧化剂	文献
磺酸酞菁铁负载于中孔分子筛	0.1 mmol/L 孔雀绿	材料+H₂O₂+可见光	光照：500 W卤灯，可见光；T=50℃；pH₀=6.0； [材料]=200 mg/L，[H₂O₂]=6.0 mmol/L	污染物：100%（1200 min） TOC：72%（1200 min）	0.00387 min^-1	HO^•	[39]
四羧基酞菁铁（3.6%（质量））负载于大孔 SiO₂	10 μmol/L 罗丹明B	材料+O₂+可见光	光照：150 W，λ≥400 nm；[材料]=1 g/L	97.4%（60 min）	0.06 min^-1	—	[40]
酞菁铁（3.8 mg Fe/g）负载于改性聚丙烯腈纤维	0.02 mmol/L 罗丹明B	材料+H₂O₂；材料+ H₂O₂+可见光	光照：9.11 mW/cm²，λ>420 nm；T=(25±1)℃； pH₀=6.0；[材料]=4 g/L，[H₂O₂]=5 mmol/L	83%（60 min） 99%（60 min）	—	Fe(Ⅳ)O、HO^•	[48]
酞菁铁负载于改性聚丙烯腈纤维	100 mg/L盐酸四环素	材料+PMS	T=298 K；pH₀=4.0；[材料]=0.5 g/L， [PMS]=2.0 mmol/L	污染物：83%（280 min） TOC：30%（280 min）	0.00035 min^-1	SO $4 • -$ 、HO^•	[4]
酞菁铁（1.47 mg Fe/g）负载于聚苯乙烯	100 mg/L盐酸土霉素	材料+ H₂O₂	T=308 K；pH₀=4.0；[材料]=0.5 g/L， [H₂O₂]=60 mmol/L	90%（500 min）	—	HO^•	[35]
酞菁铁（0.16 mmol/g）负载于改性多壁碳纳米管	0.05 mmol/L 四氯苯酚	材料+ H₂O₂	T=50℃；pH₀=7；[材料]=0.1 g/L，[H₂O₂]=5 mmol/L	100%（90 min）	0.06293 min^-1	HO^•、HOO^•	[49]
三硝基酞菁铁（2.92 mg Fe/g）负载于活性碳纤维	0.05 mmol/L磺胺甲唑	材料+ H₂O₂	T=50℃；[材料]=0.1 g/L；[H₂O₂]=20 mmol/L	99%（90 min）	—	HO^•、Fe(Ⅳ)O、HOO^•	[37]
聚酞菁铁负载于g-C₃N₄	25 μmol/L卡马西平	材料+PMS+光	光照：模拟太阳光；pH₀=7；[材料]=0.1 g/L， [PMS]=0.3 mmol/L	100%（15 min）	—	¹O₂、SO $4 • -$ 、HO^•、O $2 • -$	[43]
酞菁铁负载于TiO₂	10 mg/L甲基橙	材料+H₂O₂+可见光	光照：150 W，28 mW/cm²，λ>400 nm；T=50℃； pH₀=7；[材料]=0.5 g/L	94%（180 min）	—	HO^•	[42]
酞菁铁（0.52%（质量）Fe）负载于海绵	2 mg/L双酚A	材料+H₂O₂+紫外光	光照：紫外光，λ>150 nm；pH₀=2；[材料]=0.04 g， [H₂O₂]=0.32 mol/L	100%（20 min）	0.0918 min^-1 （20 mg/L双酚A）	HO^•	[45]
酞菁铁负载于钴尖晶石	10 mg/L罗丹明B	材料+ H₂O₂	T=25℃；[材料]=0.50 g/L，[H₂O₂]=50 mmol/L	90%（120 min）	0.02167 min^-1	O $2 • -$ 、HO^•	[41]
酞菁钴（16.5%（质量））负载于改性多壁碳纳米管	0.05 mmol/L 酸性红	材料+H₂O₂	T=50℃；pH₀=10；[材料] =0.1 g/L， [H₂O₂] =0.01 mol/L	>98%（60 min）	—	Co(Ⅳ)O	[50]
酞菁钴（14.9 μmol/g）负载于纤维素	0.05 mmol/L 酸性红	材料+ H₂O₂ 材料+PMS	T=50℃；pH₀=6.7；[材料]=2.0 g/L， [PMS]=1.0 mmol/L，[H₂O₂]=1.0 mmol/L	5%（35 min，H₂O₂体系）；100%（35 min，PMS体系）	0.0003 min^-1（H₂O₂体系）；0.0688 min^-1（PMS体系）	PMS体系：SO $4 • -$ 、HO^•；PMS+ $H C O 3 -$ 体系： Co(Ⅳ)O	[46]
酞菁钴负载于改性分子筛	5 mg/L普兰洛尔	材料+PMS	T=25℃；pH₀=5.7±0.2；[材料]=0.1 g/L， [PMS]=0.2 g/L	93.6%（30 min）	0.0920 min^-1	¹O₂、SO $4 • -$ 、HO^•	[51]
磺酸基酞菁钴（2.24% （质量））负载于TiO₂	40 mg/L 2,4- 二氯酚	材料+ H₂O₂+紫外光	光照：400 W，紫外光；pH₀=5；[材料]=0.2 g/L，[H₂O₂]=0.03 mol/L	94%（150 min）	—	$O 2 • -$ 、HO^•	[52]

Table 2 The performance of catalysts with enzyme-like active sites on the oxidative removal of contaminants

仿生材料	目标污染物	反应体系	反应条件	去除率（时间）	一级反应速率常数	活性氧化剂	文献
Fe-N₄活性中心（1.2%（质量）Fe）， g-C₃N₄基底	20 mg/L磺胺甲唑	材料+H₂O₂+可见光	光照：300 W，λ≥420 nm；pH₀=3.0；[材料]=0.2 g/L， [H₂O₂]=20 mmol/L	99.6%（40 min）	0.0535 min^-1	HO^•、O $2 • -$	[23]
Fe-N₄活性中心，g-C₃N₄、 Bi₂WO₆基底	10 mg/L 四环素	材料+H₂O₂+可见光	光照：500 W，λ>420 nm；pH₀=6.5；[材料]=0.4 g/L， [H₂O₂]=1 mmol/L	93.9%（120 min）	0.02342 min^-1	¹O₂、O $2 • -$ -	[56]
Fe-N₄活性中心（0.26%（atom）Fe），氮掺杂碳基底	0.1 mmol/L 双酚A	材料+PMS；材料+H₂O₂+可见光	T=30℃；pH₀=6.7；[材料]=0.05 g/L，[PMS]=2 mmol/L	100%（3 min）	1.99 min^-1	SO $4 • -$ 、HO^•	[59]
Fe-N₄活性中心（7.0%（质量）Fe），氮掺杂碳基底	0.1 mmol/L 4-氯酚	材料+PMS	T=20℃；[材料]=0.05 g/L，[PMS]=20 mmol/L	100%（10 min）	0.55 min^-1	¹O₂	[60]
Fe-N₄活性中心（0.81%（质量）Fe），氮掺杂碳基底	0.05 g/L 酸性橙	材料+PMS	T=25℃；pH₀=9.1；[材料]=0.1 g/L，[PMS]=0.3 g/L	100%（60 min）	0.117 min^-1	¹O₂、SO $4 • -$ 、HO^•	[61]
Fe-N₄活性中心（0.14%（质量）Fe），氮掺杂碳基底	10 mg/L磺胺甲唑	材料+PMS+可见光	光照：300 W，λ>420 nm；T=25℃；pH₀=7.0； [材料]=0.05 g/L，[PMS]=0.5 mmol/L	98.7%（6 min）	0.602 min^-1	¹O₂、HO^•、O $2 • -$ 、 Fe(Ⅳ)O	[57]
Mn-N₄活性中心，g-C₃N₄基底	2 mmol/L 草酸	材料+H₂O₂+O₃	pH₀=3；[材料]=0.1 g/L，[H₂O₂]=0.39 mmol/L， [臭氧]=30 mg/L（流量100 ml/min）	100%（45 min）	—	HO^•	[58]
Co活性中心，硼、氮掺杂碳基底	50 mg/L四环素	材料+PMS	T=25℃；pH₀=7；[材料]=0.6 g/L，[PMS]=0.6 g/L	100%（30 min）	—	¹O₂	[62]
PPyC@Py-MIL(Fe)	20 mg/L磺胺甲唑	材料+H₂O₂+可见光	光照：300 W，λ>420 nm；T=25℃；pH₀=6.5； [材料]=100 mg/L，[H₂O₂]=1 mmol/L	污染物：95%（20 min）; TOC：93%（60 min）	0.1685 min^-1 0.0434 min^-1	HO^•	[63]
Fe₃(HITP)₂ （Fe 18.1%（质量））	20 mg/L 四环素	材料+H₂O₂+可见光	光照：300 W，λ>420 nm；T=室温；pH₀=4.5； [材料]=0.4 g/L，[H₂O₂]=20 mmol/L	96.7%（30 min）	0.06 min^-1	$O 2 • -$	[64]
Pca-MIL88(Fe) （Fe 6.4%（atom））	50 mg/L 啶虫脒	材料+ H₂O₂+可见光	光照：300 W，λ>420 nm；T=25℃；[材料]=0.14 g/L， [H₂O₂]=0.006853 mol/L	污染物：100%（60 min）; TOC：97%（90 min）	0.0706 min^-1	HO^•	[65]
N-Fe-MOFs	20 mg/L 甲基橙	材料+可见光	光照：500 W，可见光；[材料]=0.8 g/L	97%（48 min）	—	光生空穴、光生电子	[66]

Table 2 The performance of catalysts with enzyme-like active sites on the oxidative removal of contaminants

仿生材料	目标污染物	反应体系	反应条件	去除率（时间）	一级反应速率常数	活性氧化剂	文献
Fe-N₄活性中心（1.2%（质量）Fe）， g-C₃N₄基底	20 mg/L磺胺甲唑	材料+H₂O₂+可见光	光照：300 W，λ≥420 nm；pH₀=3.0；[材料]=0.2 g/L， [H₂O₂]=20 mmol/L	99.6%（40 min）	0.0535 min^-1	HO^•、O $2 • -$	[23]
Fe-N₄活性中心，g-C₃N₄、 Bi₂WO₆基底	10 mg/L 四环素	材料+H₂O₂+可见光	光照：500 W，λ>420 nm；pH₀=6.5；[材料]=0.4 g/L， [H₂O₂]=1 mmol/L	93.9%（120 min）	0.02342 min^-1	¹O₂、O $2 • -$ -	[56]
Fe-N₄活性中心（0.26%（atom）Fe），氮掺杂碳基底	0.1 mmol/L 双酚A	材料+PMS；材料+H₂O₂+可见光	T=30℃；pH₀=6.7；[材料]=0.05 g/L，[PMS]=2 mmol/L	100%（3 min）	1.99 min^-1	SO $4 • -$ 、HO^•	[59]
Fe-N₄活性中心（7.0%（质量）Fe），氮掺杂碳基底	0.1 mmol/L 4-氯酚	材料+PMS	T=20℃；[材料]=0.05 g/L，[PMS]=20 mmol/L	100%（10 min）	0.55 min^-1	¹O₂	[60]
Fe-N₄活性中心（0.81%（质量）Fe），氮掺杂碳基底	0.05 g/L 酸性橙	材料+PMS	T=25℃；pH₀=9.1；[材料]=0.1 g/L，[PMS]=0.3 g/L	100%（60 min）	0.117 min^-1	¹O₂、SO $4 • -$ 、HO^•	[61]
Fe-N₄活性中心（0.14%（质量）Fe），氮掺杂碳基底	10 mg/L磺胺甲唑	材料+PMS+可见光	光照：300 W，λ>420 nm；T=25℃；pH₀=7.0； [材料]=0.05 g/L，[PMS]=0.5 mmol/L	98.7%（6 min）	0.602 min^-1	¹O₂、HO^•、O $2 • -$ 、 Fe(Ⅳ)O	[57]
Mn-N₄活性中心，g-C₃N₄基底	2 mmol/L 草酸	材料+H₂O₂+O₃	pH₀=3；[材料]=0.1 g/L，[H₂O₂]=0.39 mmol/L， [臭氧]=30 mg/L（流量100 ml/min）	100%（45 min）	—	HO^•	[58]
Co活性中心，硼、氮掺杂碳基底	50 mg/L四环素	材料+PMS	T=25℃；pH₀=7；[材料]=0.6 g/L，[PMS]=0.6 g/L	100%（30 min）	—	¹O₂	[62]
PPyC@Py-MIL(Fe)	20 mg/L磺胺甲唑	材料+H₂O₂+可见光	光照：300 W，λ>420 nm；T=25℃；pH₀=6.5； [材料]=100 mg/L，[H₂O₂]=1 mmol/L	污染物：95%（20 min）; TOC：93%（60 min）	0.1685 min^-1 0.0434 min^-1	HO^•	[63]
Fe₃(HITP)₂ （Fe 18.1%（质量））	20 mg/L 四环素	材料+H₂O₂+可见光	光照：300 W，λ>420 nm；T=室温；pH₀=4.5； [材料]=0.4 g/L，[H₂O₂]=20 mmol/L	96.7%（30 min）	0.06 min^-1	$O 2 • -$	[64]
Pca-MIL88(Fe) （Fe 6.4%（atom））	50 mg/L 啶虫脒	材料+ H₂O₂+可见光	光照：300 W，λ>420 nm；T=25℃；[材料]=0.14 g/L， [H₂O₂]=0.006853 mol/L	污染物：100%（60 min）; TOC：97%（90 min）	0.0706 min^-1	HO^•	[65]
N-Fe-MOFs	20 mg/L 甲基橙	材料+可见光	光照：500 W，可见光；[材料]=0.8 g/L	97%（48 min）	—	光生空穴、光生电子	[66]

Table 3 The performance of biomorphic catalysts or materials with catalytic environments of natural materials on the oxidative removal of contaminants

仿生材料	目标污染物	反应体系	反应条件	去除率（时间）	一级反应速度常数	活性氧化剂	文献
β-环糊精修饰的Fe₃O₄@TiO₂	20 mg/L双酚A	材料+紫外光	光照：400 W水银灯；[材料]=1 g/L	99%（60 min），100%（105 min）	—	—	[69]
β-CD修饰的TiO₂	10 mg/L亚甲基蓝	材料+可见光	光照：250 W，λ>420 nm；pH₀=7.0； [材料]=1.0 g/L	82%（10 h）	0.16105 min^-1	O $2 • -$ 、HO^•	[71]
羧甲基-β-环糊精改性的自制钛纳米管	20 mg/L 2,4-二氯苯酚 20 mg/L卡马西平 20 mg/L 双酚A 20 mg/L双酚S	材料+紫外光	光照：10 W汞灯；pH₀=4 [材料]=1 mg/ml	97.5%（150 min） 96.1%（150 min） 96.0%（150 min） 99.5%（150 min）	0.0232 min^-1 0.0261 min^-1 0.0208 min^-1 0.0399 min^-1	O $2 • -$	[72]
MnO _x 、SH-β-环糊精共修饰的金纳米团簇锚定于空心 CdS球体	20 mg/L双酚A	材料+可见光	光照：700 mW/cm²，λ>420 nm；T=25℃；pH₀=6.8；[材料]=1 mg/ml	93%（30 min）	9.04×10^-2 min^-1	HO^•	[70]
β-环糊精修饰的MnFe₂O₄	40 mg/L 2,4-二氯苯酚	材料+PMS	T=25℃；pH₀=5.98；[材料]=0.5 g/L， [PMS]=2.0 mmol/L	97%（60 min）	0.0594 min^-1	¹O₂、SO $4 • -$ 、O $2 • -$ 、HO^•	[73]
La、Fe₃O₄共负载于β-环糊精 Ce、Fe₃O₄共负载于β-环糊精	50 mg/L阳离子蓝	材料+H₂O₂	T=室温；pH₀=4；[材料]=2 g/L， [H₂O₂]=30 mmol/L	98%（20 min） 99%（10 min）	—	—	[76]
Fe₃O₄负载于β-环糊精	100 mg/L 4-氯苯	材料+H₂O₂	T=20℃；pH₀=3；[材料]=2 g/L， [H₂O₂]=30 mmol/L	100%（90 min）	0.0373 min^-1	HO^•	[75]
β-环糊精、还原氧化石墨烯共改性的Fe₃O₄	20 mg/L双酚A	材料+H₂O₂	T=25℃；pH₀=4.85；[材料]=0.5 g/L， [H₂O₂]=10 mmol/L，[NH₂OH]=4 mmol/L	100%（30 min）	0.15733 min^-1	HO^•	[74]
β-环糊精改性的生物炭	20 mg/L双酚A	材料+PDS	T=25℃；pH₀=7.0；[材料]=0.4 g/L， [PDS]=0.5 mmol/L	91.6%（30 min）	—	非自由基机制，以电子传递机制为主	[77]
以番茄皮为模板制备的CuO 负载于氧化石墨烯	100 mg/L对乙酰氨基酚	材料+高温高压	T=150℃；pH≈5.5（过程控制）；P =1.0 MPa；[材料]=0.5 g/L	污染物：96.2%（反应最后1 h）; TOC：52.1%（反应最后1 h）	—	—	[78]
具有仿生分级结构的NiO 纳米线	8.30×10^-4mol/L 亚甲基蓝	材料+紫外光	光照：30 mW/cm²，紫外光； [材料]=0.65 g/L	97%（180 min）	0.01907 min^-1	—	[33]
具有仿生减反射异质纳米结结构的ZnO纳米棒包覆硅	罗丹明6G	材料+光	光照：300 W氙灯	约100%（6 h）	—	—	[79]
TiO₂负载于金纳米棒	5 mg/L罗丹明B	材料+可见光	光照：300 W，100 mW/cm²，λ=420~780 nm；[材料]=1 g/L	98.9%（90 min）	4.98×10^-2 min^-1	—	[32]

Table 3 The performance of biomorphic catalysts or materials with catalytic environments of natural materials on the oxidative removal of contaminants

仿生材料	目标污染物	反应体系	反应条件	去除率（时间）	一级反应速度常数	活性氧化剂	文献
β-环糊精修饰的Fe₃O₄@TiO₂	20 mg/L双酚A	材料+紫外光	光照：400 W水银灯；[材料]=1 g/L	99%（60 min），100%（105 min）	—	—	[69]
β-CD修饰的TiO₂	10 mg/L亚甲基蓝	材料+可见光	光照：250 W，λ>420 nm；pH₀=7.0； [材料]=1.0 g/L	82%（10 h）	0.16105 min^-1	O $2 • -$ 、HO^•	[71]
羧甲基-β-环糊精改性的自制钛纳米管	20 mg/L 2,4-二氯苯酚 20 mg/L卡马西平 20 mg/L 双酚A 20 mg/L双酚S	材料+紫外光	光照：10 W汞灯；pH₀=4 [材料]=1 mg/ml	97.5%（150 min） 96.1%（150 min） 96.0%（150 min） 99.5%（150 min）	0.0232 min^-1 0.0261 min^-1 0.0208 min^-1 0.0399 min^-1	O $2 • -$	[72]
MnO _x 、SH-β-环糊精共修饰的金纳米团簇锚定于空心 CdS球体	20 mg/L双酚A	材料+可见光	光照：700 mW/cm²，λ>420 nm；T=25℃；pH₀=6.8；[材料]=1 mg/ml	93%（30 min）	9.04×10^-2 min^-1	HO^•	[70]
β-环糊精修饰的MnFe₂O₄	40 mg/L 2,4-二氯苯酚	材料+PMS	T=25℃；pH₀=5.98；[材料]=0.5 g/L， [PMS]=2.0 mmol/L	97%（60 min）	0.0594 min^-1	¹O₂、SO $4 • -$ 、O $2 • -$ 、HO^•	[73]
La、Fe₃O₄共负载于β-环糊精 Ce、Fe₃O₄共负载于β-环糊精	50 mg/L阳离子蓝	材料+H₂O₂	T=室温；pH₀=4；[材料]=2 g/L， [H₂O₂]=30 mmol/L	98%（20 min） 99%（10 min）	—	—	[76]
Fe₃O₄负载于β-环糊精	100 mg/L 4-氯苯	材料+H₂O₂	T=20℃；pH₀=3；[材料]=2 g/L， [H₂O₂]=30 mmol/L	100%（90 min）	0.0373 min^-1	HO^•	[75]
β-环糊精、还原氧化石墨烯共改性的Fe₃O₄	20 mg/L双酚A	材料+H₂O₂	T=25℃；pH₀=4.85；[材料]=0.5 g/L， [H₂O₂]=10 mmol/L，[NH₂OH]=4 mmol/L	100%（30 min）	0.15733 min^-1	HO^•	[74]
β-环糊精改性的生物炭	20 mg/L双酚A	材料+PDS	T=25℃；pH₀=7.0；[材料]=0.4 g/L， [PDS]=0.5 mmol/L	91.6%（30 min）	—	非自由基机制，以电子传递机制为主	[77]
以番茄皮为模板制备的CuO 负载于氧化石墨烯	100 mg/L对乙酰氨基酚	材料+高温高压	T=150℃；pH≈5.5（过程控制）；P =1.0 MPa；[材料]=0.5 g/L	污染物：96.2%（反应最后1 h）; TOC：52.1%（反应最后1 h）	—	—	[78]
具有仿生分级结构的NiO 纳米线	8.30×10^-4mol/L 亚甲基蓝	材料+紫外光	光照：30 mW/cm²，紫外光； [材料]=0.65 g/L	97%（180 min）	0.01907 min^-1	—	[33]
具有仿生减反射异质纳米结结构的ZnO纳米棒包覆硅	罗丹明6G	材料+光	光照：300 W氙灯	约100%（6 h）	—	—	[79]
TiO₂负载于金纳米棒	5 mg/L罗丹明B	材料+可见光	光照：300 W，100 mW/cm²，λ=420~780 nm；[材料]=1 g/L	98.9%（90 min）	4.98×10^-2 min^-1	—	[32]

Table 4 The performance of biomimetic materials on the reductive removal of contaminants

仿生材料	目标污染物	主要产物	反应体系	反应条件	去除率（时间）	一级反应速率常数	文献
Mo、双齿氮配体、Pd 共负载的碳材料	1 mmol/L NaClO₄	Cl^-	材料+H₂（电子供体）	T=20℃；pH=2.9~3.0（过程控制）； [材料]=0.2 g/L，[H₂]=0.1 MPa	100% （60 min）	0.0251 min^-1	[81]
Fe、Co、N共掺杂的碳材料	10 mg/L Cr(Ⅵ)	Cr(Ⅲ)	材料+甲酸（电子供体）	T=25℃；pH₀=1.74；[甲酸]=0.234 mol/L， [材料]=0.05 g/L	100% （105 min）	0.269 min^-1	[80]
Au负载于β-环糊精	5.64×10^-4 mol/L 4-硝基苯酚	4-氨基苯酚	材料+硼氢化钠（电子供体）	T=室温；[材料]=20 mg，[NaBH₄]=0.495 mol/L	—	0.1415 s^-1	[82]
β-环糊精修饰的MoS₂、g-C₃N₄构成的复合材料	10 mg/L Cr(Ⅵ)	Cr(Ⅲ)	材料+光	光照：1000 mW，模拟太阳光；[材料]=0.4 g/L，[EDTA-2Na]=0.4 mmol/L	76% （50 min）	—	[83]
Co（1.4%（质量））、 N、B共掺杂的碳材料	50 mg/L氯霉素	—	三电极系统	电压：-0.9V vs AgCl；电极尺寸：1.0 cm×2.5 cm；对电极：铂丝，参比电极：Ag/AgCl，工作电极：碳纤维纸（负载0.32 mg/cm²材料）；电解液：0.067 mol/L Na₂HPO₄和KH₂PO₄；pH₀=7	100% （3 h）	1.6963 h^-1	[84]
Fe、N共掺杂的碳材料	25 μmol/L三氯乙烯	乙烷、乙烯	三电极系统	电压：-1.2 V vs AgCl；电极尺寸：2 cm×2 cm；对电极（阳极）：Pt，参比电极：Ag/AgCl，工作电极（阴极）：玻碳电极（负载材料）；电解质：2 mmol/L Na₂SO₄；pH₀=7.0	94% （8 h）	0.36 h^-1	[85]
Fe、N、S共掺杂的碳材料	100 mg N/L $N O 3 -$	N₂、 $N H 4 +$	三电极系统	电压：-0.67 V vs RHE；阳极：Ti/IrO₂-Ru，参比电极：Ag/AgCl，工作电极：材料；电解质：100 mg N/L硝酸盐溶液、0.02 mol/L Na₂SO₄或NaCl；pH=6.7~7.8（过程控制）	—	2.3×10^-3 h^-1	[86]
Fe、N共掺杂的碳材料	0.5 mol/L KNO₃	—	三电极系统	电压：-0.85 V vs RHE；电流：100 mA/cm²；电极尺寸：1 cm×2 cm，浸泡尺寸：1 cm×1 cm；参比电极：饱和甘汞电极;对电极：铂箔;工作电极：铂碳电极（负载0.4 mg/cm²催化剂）；电解质：0.1 mol/L K₂SO₄、0.5 mol/L KNO₃	—	—	[87]

Table 4 The performance of biomimetic materials on the reductive removal of contaminants

仿生材料	目标污染物	主要产物	反应体系	反应条件	去除率（时间）	一级反应速率常数	文献
Mo、双齿氮配体、Pd 共负载的碳材料	1 mmol/L NaClO₄	Cl^-	材料+H₂（电子供体）	T=20℃；pH=2.9~3.0（过程控制）； [材料]=0.2 g/L，[H₂]=0.1 MPa	100% （60 min）	0.0251 min^-1	[81]
Fe、Co、N共掺杂的碳材料	10 mg/L Cr(Ⅵ)	Cr(Ⅲ)	材料+甲酸（电子供体）	T=25℃；pH₀=1.74；[甲酸]=0.234 mol/L， [材料]=0.05 g/L	100% （105 min）	0.269 min^-1	[80]
Au负载于β-环糊精	5.64×10^-4 mol/L 4-硝基苯酚	4-氨基苯酚	材料+硼氢化钠（电子供体）	T=室温；[材料]=20 mg，[NaBH₄]=0.495 mol/L	—	0.1415 s^-1	[82]
β-环糊精修饰的MoS₂、g-C₃N₄构成的复合材料	10 mg/L Cr(Ⅵ)	Cr(Ⅲ)	材料+光	光照：1000 mW，模拟太阳光；[材料]=0.4 g/L，[EDTA-2Na]=0.4 mmol/L	76% （50 min）	—	[83]
Co（1.4%（质量））、 N、B共掺杂的碳材料	50 mg/L氯霉素	—	三电极系统	电压：-0.9V vs AgCl；电极尺寸：1.0 cm×2.5 cm；对电极：铂丝，参比电极：Ag/AgCl，工作电极：碳纤维纸（负载0.32 mg/cm²材料）；电解液：0.067 mol/L Na₂HPO₄和KH₂PO₄；pH₀=7	100% （3 h）	1.6963 h^-1	[84]
Fe、N共掺杂的碳材料	25 μmol/L三氯乙烯	乙烷、乙烯	三电极系统	电压：-1.2 V vs AgCl；电极尺寸：2 cm×2 cm；对电极（阳极）：Pt，参比电极：Ag/AgCl，工作电极（阴极）：玻碳电极（负载材料）；电解质：2 mmol/L Na₂SO₄；pH₀=7.0	94% （8 h）	0.36 h^-1	[85]
Fe、N、S共掺杂的碳材料	100 mg N/L $N O 3 -$	N₂、 $N H 4 +$	三电极系统	电压：-0.67 V vs RHE；阳极：Ti/IrO₂-Ru，参比电极：Ag/AgCl，工作电极：材料；电解质：100 mg N/L硝酸盐溶液、0.02 mol/L Na₂SO₄或NaCl；pH=6.7~7.8（过程控制）	—	2.3×10^-3 h^-1	[86]
Fe、N共掺杂的碳材料	0.5 mol/L KNO₃	—	三电极系统	电压：-0.85 V vs RHE；电流：100 mA/cm²；电极尺寸：1 cm×2 cm，浸泡尺寸：1 cm×1 cm；参比电极：饱和甘汞电极;对电极：铂箔;工作电极：铂碳电极（负载0.4 mg/cm²催化剂）；电解质：0.1 mol/L K₂SO₄、0.5 mol/L KNO₃	—	—	[87]

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