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

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

Chinese Journal of Catalysis ›› 2024, Vol. 60: 128-157.DOI: 10.1016/S1872-2067(24)60016-1

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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)

Abstract

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

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]

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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