相变储热材料强化催化反应过程的研究进展

doi:10.1016/S1872-2067(24)60016-1

催化学报 ›› 2024, Vol. 60: 128-157.DOI: 10.1016/S1872-2067(24)60016-1

相变储热材料强化催化反应过程的研究进展

王长安^a, 欧阳颖^b, 罗一斌^b^,^*(), 高心茹^a, 高鸿毅^a^,^c^,^*(), 王戈^a^,^d^,^*(), 舒兴田^b^,^*()

^a北京科技大学材料科学与工程学院, 北京材料基因工程高精尖创新中心,分子与微结构可控材料北京市重点实验室, 北京 100083
^b中石化石油化工科学研究院有限公司, 北京 100083
^c中国石油化工股份有限公司长岭分公司, 湖南岳阳 414012
^d北京科技大学顺德创新学院, 广东顺德 528399

收稿日期:2024-01-16 接受日期:2024-02-27 出版日期:2024-05-18 发布日期:2024-05-20
通讯作者: *电子信箱: hygao@ustb.edu.cn (高鸿毅), luoyibin.ripp@sinopec.com (罗一斌), gewang@ustb.edu.cn (王戈), shuxingtian.ripp@sinopec.com (舒兴田).
基金资助:
广东省基础与应用基础研究基金项目;广东省基础与应用基础研究基金项目(2022A1515011918);北京市自然科学基金(L233011)

Review on recent advances in phase change materials for enhancing the catalytic process

Chang’an Wang^a, Ying Ouyang^b, Yibin Luo^b^,^*(), Xinru Gao^a, Hongyi Gao^a^,^c^,^*(), Ge Wang^a^,^d^,^*(), Xingtian Shu^b^,^*()

^aBeijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
^bResearch Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
^cSINOPEC Changling Branch Company, Yueyang 414012, Hunan, China
^dShunde Innovation School, University of Science and Technology Beijing, Shunde 528399, Guangdong, China

Received:2024-01-16 Accepted:2024-02-27 Online:2024-05-18 Published:2024-05-20
Contact: *E-mail: hygao@ustb.edu.cn (H. Gao), luoyibin.ripp@sinopec.com (Y. Luo), gewang@ustb.edu.cn (G. Wang), shuxingtian.ripp@sinopec.com (X. Shu).
About author:Yibin Luo is a professor at Research Institute of Petroleum Processing, SINOPEC. Dr. Luo has more than 30 yr of experience on zeolite synthesis and industrial applications in both petroleum refining and chemical production. He led the team to develop various series of zeolites, which were formulated into nearly 200,000 tons/year of catalysts used in catalytic cracking units. He has been granted 46 Chinese invention patents and published more than 30 peer‐reviewed papers.
Hongyi Gao (Beijing Advanced Innovation Center for Materials Genome Engineering, School of Materials Science and Engineering, University of Science and Technology Beijing) received his Ph.D. in Materials Physics and Chemistry, University of Science and Technology Beijing in 2015. He then worked as a postdoc fellow in the School of Energy and Environmental Engineering at University of Science and Technology Beijing from 2015 to 2017. He is now an associate professor at University of Science and Technology Beijing. His current research focuses on synthesis and application of MOFs based energy storage and conversion materials and heterogeneous catalysts. He has published more than 100 peer-reviewed papers.
Ge Wang (Beijing Advanced Innovation Center for Materials Genome Engineering, School of Materials Science and Engineering, University of Science and Technology Beijing) received her Ph.D. in Chemistry from the Michigan Technological University in 2002. Currently she is a professor and Ph.D. supervisor in the School of Material Science and Engineering at the University of Science and Technology Beijing. In 2012, she became a special chair professor endowed by the Chang Jiang Scholars Program of the Ministry of Education. Her research interests focus on creating complex materials structures with nanoscale precision using chemical approaches, and studying the functionalities including catalytic, energy storage and energy saving properties etc. She has published more than 300 peer‐reviewed papers.
Xingtian Shu (Research Institute of Petroleum Processing, SINOPEC, Beijing, China) is a professor and a member of the Chinese Academy of Engineering. He has more than 50 yr of experience on exploring novel zeolite-based catalysts for efficient petroleum refining and chemical production processes. He has been granted more than 200 Chinese invention patents and published more than 50 peer‐reviewed papers.
Supported by:
SINOPEC Research Institute of Petroleum Processing;Guangdong Basic and Applied Basic Research Foundation(2022A1515011918);Beijing Natural Science Foundation(L233011)

摘要/Abstract

摘要：

催化过程在化工生产中起着至关重要的作用, 开发高性能催化材料是提升催化效率的有效策略之一. 然而, 多数催化过程伴随的强烈放热或吸热效应往往影响材料的催化效率, 甚至可能导致失活. 近年来, 相变储热材料(PCMs)因具有较好的热管理和能量存储性能, 在热催化、光催化、生物催化和电化学领域展现出广阔的应用潜力. 将PCMs与催化材料相结合, 形成PCMs@Catalysts复合材料, 可以提升能源利用效率和强化催化反应过程. 利用微胶囊技术, 可以实现这种复合材料的储热区及催化区的分区组装及功能集成, 其中催化材料壳层不仅增强了PCMs热导率和稳定性, 还能够有效防止PCMs相变过程的泄漏. 同时, PCMs芯材通过吸收/释放反应过程的热量和控制壳层催化材料的温度达到提升催化效率的目的. 本综述旨在深入介绍相变材料在强化催化反应方面的最新进展, 并为PCMs@Catalysts复合材料的理性设计和可控制备提出见解.

本文系统地总结了PCMs@Catalysts复合材料的制备方法及其在热催化、光催化、生物催化和电化学领域的应用进展. PCMs@Catalysts的制备方法主要包括物理法和化学法. 物理法, 如喷雾干燥法和空气悬浮法, 主要通过物理手段将外壳溶液均匀地包覆在PCMs内核表面, 形成厚度适中的外壳. 而化学法, 如原位聚合法、原位沉淀法、悬浮聚合法、诱导氧化法和溶胶-凝胶法等, 则通过在PCMs表面原位生长致密的氧化物壳层来实现复合材料的构筑. 在应用方面, PCMs组分提升催化反应性能的作用机制主要包括以下三种. (1) 自蓄热驱动催化效应: PCMs材料在催化反应中高效储存来自环境余热或太阳能等外界热源的热能, 并在移除热源后持续稳定地释放潜热以驱动催化反应的进行. (2)原位温度调节效应: 由PCMs芯材存储反应过程中的热量以调节催化材料壳层微环境温度, 进而调控催化剂床层温度, 防止催化过程热失控并延长催化剂使用寿命. (3)热流/电子协同效应: PCMs释放的热流能够加速催化材料表面底物分子的热运动和光生电子/空穴的迁移, 进而克服反应物转化的能量势垒; 热流和光生电荷的协同效应有助于提高太阳能的利用率和反应物的转化率.

综上, 本文系统地总结了PCMs@Catalysts复合材料的合成制备方法、协同作用机制及其在不同催化领域的应用进展. 展望未来, PCMs@Catalysts复合材料研究应在保证其综合力学性能的基础上, 进一步提高催化性能和储/放热效率. 本文旨在为PCMs@Catalysts的理性设计和精准构筑提供参考, 也为其在工业领域的规模化应用提供借鉴.

关键词: 相变储热材料, 催化剂, 微胶囊技术, 催化性能, 协同效应

Abstract:

Catalysis plays a critical role in almost every industrial process, and developing high-performance catalyst is one of the most efficient strategies for enhancing the catalytic process. However, most of the catalytic processes involve the heat release or absorption effect, which would influence the catalytic efficiency and even result in the deactivation of the catalyst. Recently, phase change materials (PCMs) have demonstrated unique potential for enhancing the catalytic process in thermocatalytic, photocatalytic, biocatalytic and electrochemical fields due to the thermal management and energy storage functions. The innovative integration of PCMs and catalysts can simultaneously raise energy efficiency and enhance the catalytic process. Microencapsulation technology enables the in-situ coupling of PCMs within catalysts, and the introduction of encapsulated shells or nanoparticles with catalytic effects endows the PCMs with good chemical stability, thermal cycling stability as well as high thermal conductivity. The synergistic mechanism between catalysts and PCMs in different systems can be summarized as self-stored thermal driven catalysis, in-situ temperature regulation and heat flow/electron synergistic effect. In addition, the correlation between the microstructure and catalytic/thermal management performance of PCMs@Catalysts composites was systematically discussed. Finally, the current challenges and development trends of the multifunctional PCMs@Catalysts composites are also presented. The review aims to highlight recent advances in phase change materials for enhancing the catalytic process and provide insights into the rational design and controllable preparation of PCMs@Catalysts composites.

Key words: Phase change materials, Catalyst, Microencapsulation, Catalytic performance, Synergistic mechanism

王长安, 欧阳颖, 罗一斌, 高心茹, 高鸿毅, 王戈, 舒兴田. 相变储热材料强化催化反应过程的研究进展[J]. 催化学报, 2024, 60: 128-157.

Chang’an Wang, Ying Ouyang, Yibin Luo, Xinru Gao, Hongyi Gao, Ge Wang, Xingtian Shu. Review on recent advances in phase change materials for enhancing the catalytic process[J]. Chinese Journal of Catalysis, 2024, 60: 128-157.

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PCMs@ Catalysts	Synthesis method	Shell layer	PCMs core	Catalyst	Melting/ Freezing enthalpy (J/g)	Melting/ Crystallization temperature (°C)	Encapsulation rate (%)	Reaction	Ref.
Ni/Al₂O₃/NaCl Ni/ZrO₂/ Na₂CO₃	impregnation method + melt impregnation method	Ni + Al₂O₃ Ni + ZrO₂	NaCl Na₂CO₃	Ni	—/220	—	—	solar thermochemical reforming of methane	[67]
Ni/MEPCM	boehmite treatment + precipitation treatment + thermal oxidation treatment	NiO + α-Al₂O₃	Al-Si	NiO	177.84/—	573.43/—	—	CO₂ methanation	[71]
(Fe₂O₃/Al₂O₃)/ (Al@Al₂O₃)	thermal oxidation + gelation method	Fe₂O₃/Al₂O₃	Al@Al₂O₃	Fe₂O₃	~180/~185	~660/~610	—	unsteady-state chemical reaction	[73]
Co₃O₄/ (SiAl@Al₂O₃)	induced oxidation method+ Co-precipitation method	Co₃O₄ + α-Al₂O₃	Al-Si	Co₃O₄	~100/~80	577/550	—	methane combustion	[45]
Al@Al₂O₃-C	induced oxidation method + in-situ decomposition method	Al₂O₃ + Ni + C	Al	—	267.6/266.3	660.3/628.3	—	high-temperature catalysis industry	[61]
α-Al₂O₃@Al-Si	boehmite treatment + thermal oxidation method	α-Al₂O₃	Al-Si	—	247/—	573/—	57	S-IGFC, A-IGCC and A-IGFC	[60]
MEPCMs	ultrasonic polymerization + self-assembly method + solution combustion synthesis	CaCO₃-PMMA	Sn	Ce, Mn	56.31/51.21	231.8/154.8	77.3	industrial denitrification/desulphurisation	[59]
SiO₂/poly(EGDMA-co-MAA)@n-eicosane	emulsion-template interfacial condensation method + surface free-radical polymerization	SiO₂ + poly(EGDMA-co-MAA)	n-eicosane	recognition sites	165.3/164.1	~37/~29	63.4	adsorption of BPA	[81]
Pt/ SiO₂ In@SiO₂ paraffin@SiO₂	sol-gel method + impregnation method	SiO₂	In or paraffin	Pt	160 (Encapsulated paraffin)/ ——	—	~80 (encapsulated paraffin)	methanol oxidation, MMA polymerization	[30]
SiO₂@n-octadecane	sol-gel method	SiO₂	n-octadecane	—	129.1/121.3	27.23/24.37	54.5	esterification of propionic anhydride and n-butanol	[82]

PCMs@ Catalysts	Synthesis method	Shell layer	PCMs core	Catalyst	Melting/ Freezing enthalpy (J/g)	Melting/ Crystallization temperature (°C)	Encapsulation rate (%)	Reaction	Ref.
Ni/Al₂O₃/NaCl Ni/ZrO₂/ Na₂CO₃	impregnation method + melt impregnation method	Ni + Al₂O₃ Ni + ZrO₂	NaCl Na₂CO₃	Ni	—/220	—	—	solar thermochemical reforming of methane	[67]
Ni/MEPCM	boehmite treatment + precipitation treatment + thermal oxidation treatment	NiO + α-Al₂O₃	Al-Si	NiO	177.84/—	573.43/—	—	CO₂ methanation	[71]
(Fe₂O₃/Al₂O₃)/ (Al@Al₂O₃)	thermal oxidation + gelation method	Fe₂O₃/Al₂O₃	Al@Al₂O₃	Fe₂O₃	~180/~185	~660/~610	—	unsteady-state chemical reaction	[73]
Co₃O₄/ (SiAl@Al₂O₃)	induced oxidation method+ Co-precipitation method	Co₃O₄ + α-Al₂O₃	Al-Si	Co₃O₄	~100/~80	577/550	—	methane combustion	[45]
Al@Al₂O₃-C	induced oxidation method + in-situ decomposition method	Al₂O₃ + Ni + C	Al	—	267.6/266.3	660.3/628.3	—	high-temperature catalysis industry	[61]
α-Al₂O₃@Al-Si	boehmite treatment + thermal oxidation method	α-Al₂O₃	Al-Si	—	247/—	573/—	57	S-IGFC, A-IGCC and A-IGFC	[60]
MEPCMs	ultrasonic polymerization + self-assembly method + solution combustion synthesis	CaCO₃-PMMA	Sn	Ce, Mn	56.31/51.21	231.8/154.8	77.3	industrial denitrification/desulphurisation	[59]
SiO₂/poly(EGDMA-co-MAA)@n-eicosane	emulsion-template interfacial condensation method + surface free-radical polymerization	SiO₂ + poly(EGDMA-co-MAA)	n-eicosane	recognition sites	165.3/164.1	~37/~29	63.4	adsorption of BPA	[81]
Pt/ SiO₂ In@SiO₂ paraffin@SiO₂	sol-gel method + impregnation method	SiO₂	In or paraffin	Pt	160 (Encapsulated paraffin)/ ——	—	~80 (encapsulated paraffin)	methanol oxidation, MMA polymerization	[30]
SiO₂@n-octadecane	sol-gel method	SiO₂	n-octadecane	—	129.1/121.3	27.23/24.37	54.5	esterification of propionic anhydride and n-butanol	[82]

PCMs@Catalysts	Synthesis method	Shell layer	PCM core	Catalyst	Melting/ freezing enthalpy (J/g)	Melting/ Crystallization temperature (°C)	Encapsulation rate (%)	Reaction	Ref.
Ag-Paraffin @Halloysite	self-assembly method	Ag + Halloysite	paraffin	Ag	150.58/ 136.42	61.82/57.93	87.4	4-nitrophenol reduction	[44]
TiO₂/poly(4-MeS-co-DVB)@hexadecane	one-pot non-Pickering emulsion templated suspension polymerization method	TiO₂ + [poly(4- ethylstyrene-co- divinylbenzene)]	hexadecane	TiO₂	182.0±3/ 174.0±3	17.5±0.3/ —	76.6	methylene blue degradation	[87]
TiO₂@ n-eicosane	sol-gel method + in-situ polycondensation	TiO₂	n-eicosane	TiO₂	97.6/ 95.33	43.88/35.39	49.9	methylene blue degradation	[64]
n-eicosane@ TiO₂@graphene	interfacial polycondensation + surface self-assembly	graphene + TiO₂	paraffin	TiO₂	~162/ ~160	~40/~33	65.59	methyl blue degradation	[54]
ZnO@n-eicosane	in-situ precipitation method	ZnO	n-eicosane	ZnO	50‒135/ 28‒133	38~40/ 29~31	35~70	methylene blue degradation	[31]
ZnO/SiO₂@ n-docosane	emulsion-templated interfacial condensation + structure-induced growth method	ZnO + SiO₂	n-docosane	ZnO	139/~137	~44/~35	~60	—	[88]
TiO₂/poly(HDDA)@paraffin	microfluidic emulsification + on-the-fly photopolymerization	poly(1,6-hexanediol diacrylate) + TiO₂	paraffin	TiO₂	—	—	—	methylene blue degradation	[89]
paraffin@SiO₂/ FeOOH	interfacial condensation method	FeOOH + SiO₂	paraffin	FeOOH	104.44/ 101.69	26.1/25.49	49.68	methylene blue degradation	[90]
TiO₂@SnBi58	ultrasonic polymerization + liquid-phase precipitation method	TiO₂	SnBi58	TiO₂	46.61/ 37.57	137.6/132.1	—	methylene blue degradation	[91]
TiO₂-polyurethane@butyl stearate	interfacial polymerization method	TiO₂-polyurethane	butyl stearate	TiO₂	16.75/—	26/—	—	MO degradation	[92]
Cu₂O@n-eicosane	emulsion template self-assembly method + in-situ precipitation	Cu₂O	n-eicosane	Cu₂O	165.3/ 163.1	38.71/32.52	61.61	degradation of malachite green, acid fuchsin, Congo red	[49]
SiO₂/TiO₂/PDA@n-eicosane	interfacial polycondensation method + sol-gel method	SiO₂/TiO₂/PDA	n-eicosane	TiO₂	~125/ ~125	~43/~35	—	RhB degradation	[65]
n-eicosane/TiO₂-based microcapsules	emulsion-templated interfacial polycondensation method	TiO₂	n-eicosane	TiO₂	~185/ ~180	~41.8/~30	75.9	RhB degradation	[93]
PDVB/TiO₂@ paraffin	pickering emulsion polymerization method	TiO₂ + PDVB	paraffin	TiO₂	139.1/ 140.8	26.6/23.5	78.9	HCHO decomposition	[94]
D-P@Ce-Eu/ TiO₂	interfacial condensation + vacuum impregnation	Ce-Eu/TiO₂	DA-PA	Ce-Eu/ TiO₂	—	—	—	HCHO decomposition	[66]
PA-DA@ Ce-Eu/TiO₂	interfacial condensation + vacuum impregnation method	Ce-Eu/TiO₂	PA-DA	Ce-Eu/ TiO₂	64.6/59.1	27.54/17.12	—	HCHO decomposition	[95]
C18@titania	aerosol process + hydro thermal post-treatment	TiO₂	n- octadecane	TiO₂	97/92	28.7/21	—	CH₃SH decomposition	[96]

PCMs@Catalysts	Synthesis method	Shell layer	PCM core	Catalyst	Melting/ freezing enthalpy (J/g)	Melting/ Crystallization temperature (°C)	Encapsulation rate (%)	Reaction	Ref.
Ag-Paraffin @Halloysite	self-assembly method	Ag + Halloysite	paraffin	Ag	150.58/ 136.42	61.82/57.93	87.4	4-nitrophenol reduction	[44]
TiO₂/poly(4-MeS-co-DVB)@hexadecane	one-pot non-Pickering emulsion templated suspension polymerization method	TiO₂ + [poly(4- ethylstyrene-co- divinylbenzene)]	hexadecane	TiO₂	182.0±3/ 174.0±3	17.5±0.3/ —	76.6	methylene blue degradation	[87]
TiO₂@ n-eicosane	sol-gel method + in-situ polycondensation	TiO₂	n-eicosane	TiO₂	97.6/ 95.33	43.88/35.39	49.9	methylene blue degradation	[64]
n-eicosane@ TiO₂@graphene	interfacial polycondensation + surface self-assembly	graphene + TiO₂	paraffin	TiO₂	~162/ ~160	~40/~33	65.59	methyl blue degradation	[54]
ZnO@n-eicosane	in-situ precipitation method	ZnO	n-eicosane	ZnO	50‒135/ 28‒133	38~40/ 29~31	35~70	methylene blue degradation	[31]
ZnO/SiO₂@ n-docosane	emulsion-templated interfacial condensation + structure-induced growth method	ZnO + SiO₂	n-docosane	ZnO	139/~137	~44/~35	~60	—	[88]
TiO₂/poly(HDDA)@paraffin	microfluidic emulsification + on-the-fly photopolymerization	poly(1,6-hexanediol diacrylate) + TiO₂	paraffin	TiO₂	—	—	—	methylene blue degradation	[89]
paraffin@SiO₂/ FeOOH	interfacial condensation method	FeOOH + SiO₂	paraffin	FeOOH	104.44/ 101.69	26.1/25.49	49.68	methylene blue degradation	[90]
TiO₂@SnBi58	ultrasonic polymerization + liquid-phase precipitation method	TiO₂	SnBi58	TiO₂	46.61/ 37.57	137.6/132.1	—	methylene blue degradation	[91]
TiO₂-polyurethane@butyl stearate	interfacial polymerization method	TiO₂-polyurethane	butyl stearate	TiO₂	16.75/—	26/—	—	MO degradation	[92]
Cu₂O@n-eicosane	emulsion template self-assembly method + in-situ precipitation	Cu₂O	n-eicosane	Cu₂O	165.3/ 163.1	38.71/32.52	61.61	degradation of malachite green, acid fuchsin, Congo red	[49]
SiO₂/TiO₂/PDA@n-eicosane	interfacial polycondensation method + sol-gel method	SiO₂/TiO₂/PDA	n-eicosane	TiO₂	~125/ ~125	~43/~35	—	RhB degradation	[65]
n-eicosane/TiO₂-based microcapsules	emulsion-templated interfacial polycondensation method	TiO₂	n-eicosane	TiO₂	~185/ ~180	~41.8/~30	75.9	RhB degradation	[93]
PDVB/TiO₂@ paraffin	pickering emulsion polymerization method	TiO₂ + PDVB	paraffin	TiO₂	139.1/ 140.8	26.6/23.5	78.9	HCHO decomposition	[94]
D-P@Ce-Eu/ TiO₂	interfacial condensation + vacuum impregnation	Ce-Eu/TiO₂	DA-PA	Ce-Eu/ TiO₂	—	—	—	HCHO decomposition	[66]
PA-DA@ Ce-Eu/TiO₂	interfacial condensation + vacuum impregnation method	Ce-Eu/TiO₂	PA-DA	Ce-Eu/ TiO₂	64.6/59.1	27.54/17.12	—	HCHO decomposition	[95]
C18@titania	aerosol process + hydro thermal post-treatment	TiO₂	n- octadecane	TiO₂	97/92	28.7/21	—	CH₃SH decomposition	[96]

PCMs@ Catalysts	Synthesis method	Shell layer	PCM core	Active component	Melting/ freezing enthalpy (J/g)	Melting/crystalli zation temperature (°C)	Encapsulation rate (%)	Reaction	Ref.
MEPCM- PANI/PR	emulsion-templated interfacial condensation + in-situ oxidation polymerization	PANI/PR/ SiO₂	n-docosane	PANI	~120/~120	~45/~34	50.2	supercapacitors	[55]
MnO₂/SiO₂@ n-docosane	interfacial condensation + template-directed self-assembly method	MnO₂/ SiO₂	n-docosane	MnO₂	~175/~170	~46/~35	63.1		[35]
Ni(OH)₂-SiO₂-MEPCM	emulsion-templated interfacial condensation + structure-directed interfacial precipitation	Ni(OH)₂- SiO₂	n-docosane	Ni(OH)₂	140.52/139.1	48.56/31.29	59.97		[16]
MEPCM- PANi/CNTs	emulsion-templated interfacial polycondensation + in-situ oxidative polymerization	PANi/ CNTs/SiO₂	n-docosane	PANi/CNTs	142.7/143.2	45.6/34.2	61.2		[101]
CNF/GP/ MPCMs	in-situ polymerization + one-pot electrochemical co-deposition method	melamine resin	n- octadecane	PANi/CNF	201.63/199.54	~30/~10	81.18		[100]
OA-PEG/ SiO₂/SnO₂ NEPCMs	in-situ emulsion interfacial hydrolysis + polycondensation + ionic layer adsorption	SnO₂/SiO₂	oleic acid - polyethylene glycol	SnO₂	58.79/55.49	3.11/2.57	52.12	electrode reaction	[34]

相变储热材料强化催化反应过程的研究进展

Review on recent advances in phase change materials for enhancing the catalytic process

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PCMs@ Catalysts	Synthesis method	Shell layer	PCM core	Catalyst	Melting/ freezing enthalpy (J/g)	Melting/ crystallization temperature (°C)	Encapsulation rate (%)	Reaction	Ref.
Ag/SiO₂@ n-eicosane	interfacial condensation + silver reduction method	Ag/SiO₂	n-eicosane	Ag	~155/ ~153	~40/~32.5	67	inactivation of Staphylococcus aureus and Bacillus subtilis	[36]
Ag/SiO₂-MicroPCMs	photocurable pickering emulsion polymerization + silver reduction method	Ag/SiO₂-PMMA	n- octadecane	Ag	110.76/ ~110	~25/~14	—	inactivation of staphylococcus aureus	[102]
α-amylase/Fe₃O₄/SiO₂@n-docosane	pickering emulsion-templated suspension polymerization	α-amylase /Fe₃O₄/SiO₂	n-docosane	α- amylase	157.6/ 156.3	44.9/35.2	58	starch decomposition	[103]
CRL/TiO₂/Fe₃O₄@n-eicosane	pickering emulsion templating self-assembly + interfacial polycondensation	CRL/TiO₂ /Fe₃O₄	n-eicosane	CRL	138.3/ 137.6	38.6/32.4	51.36	hydrolysis of olive oil	[37]
Pen X-CS@SiO₂-MEPCM	emulsion-templated interfacial poly-condensation	Pen X/CS/SiO₂	n-docosane	Pen X	127.2/ 125.2	44.5/35.1	54.7	hydrolysis of penicillin	[105]
LA-Au/ PDA@SiO₂- MEPCM	surfactant-assisted self-assembly + in-situ reduction + immobilized copper chelate method	LA-Au/PDA @SiO₂	n-docosane	LA	~120/ ~120	~45/~35	51.5	ABTS oxidation	[106]
ZIF-8@PPy- SiO₂-MEPCM	emulsion-templated interfacial condensation + oxidative polymerization reaction	ZIF-8@ PPy-SiO₂	n-docosane	LA+ ZIF-8	>120/>120	~45/~34	>51	dopamine detection	[38]
HRP@PPy- TiO₂-MEPCM	emulsion-templated interfacial condensation + oxidative polymerization reaction + physical adsorption	HRP@ PPy-TiO₂	n-eicosane	HRP	~115/~115	~37/~26	>51	catechol detection	[39]
Tyr-Fe₃O₄/PPy@TiO₂@n-C₂₀ MEPCM	emulsion-templated interfacial polycondensation + surfactant-assisted self-assembly + oxidation polymerization	Tyr/Fe₃O₄/ PPy/TiO₂	n-eicosane	tyrosinase	153.1/149.0	37.85/28.28	71.90	catechol detection	[109]

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