Exsolved metal nanoparticles on perovskite oxides: exsolution, driving force and control strategy

doi:10.16085/j.issn.1000-6613.2022-1418

Abstract

Abstract:

Supported metal nanoparticles have been widely applied in catalytic processes related to energy conversion and storage. However, the size and distribution of metal nanoparticles prepared by impregnation and deposition are difficult to control. The metal nanoparticles catalysts are often deactivated due to sintering, carbon deposition and other problems in operation. The exsolution strategy is expected to provide a feasible way to solve the above problems. The exsolved metal nanoparticles are embedded and evenly distributed on the surface of the oxide matrix, which can provide a strong metal-support interaction and effectively alleviate sintering and coking. Based on the metal exsolution of perovskites, this paper summarizes the characteristics and formation process of exsolved metal nanoparticles and introduced the driving forces of oxygen vacancy, phase transition and Gibbs free energy in the exsolution process. Then, the effective methods to control exsolution are proposed from the characteristics of the matrix and the reduction conditions. Finally, the application progress of exsolution strategy is discussed. However, the exsolution mechanism and properties regulation of metal nanoparticles needed to be further studied by combining in situ characterization technology and theoretical calculation. This paper provides an important reference for optimizing the surface properties of metal nanoparticles and developing high-performance catalysts.

Key words: nanoparticles, metal exsolution, perovskites, oxygen vacancy, phase transition, catalysis

摘要：

负载型金属纳米粒子已广泛应用在与能量转化及储存相关的催化过程。但是，浸渍、沉积法制备的金属纳米粒子尺寸和分布难以控制，在应用中易因烧结、积炭等问题失活。溶出策略制备的金属纳米粒子镶嵌在母体表面，尺寸均匀，具有更强的金属-载体作用，为解决上述问题提供了一条可行之路。本文从钙钛矿的溶出现象出发，综述了金属纳米粒子的溶出过程及其应用优势，并介绍了氧空位、相变和吉布斯自由能在溶出中的驱动作用。然后，从材料自身特性和还原条件阐明了溶出控制策略。最后总结了溶出型催化剂的应用进展。然而，在金属粒子溶出机制、性质调控方面，仍需结合原位技术和理论计算进行深入研究。

关键词: 纳米粒子, 金属溶出, 钙钛矿, 氧空位, 相变, 催化

CLC Number:

TQ426.8

DONG Xiaoshan, WANG Jian, LIN Fawei, YAN Beibei, CHEN Guanyi. Exsolved metal nanoparticles on perovskite oxides: exsolution, driving force and control strategy[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3049-3065.

董晓珊, 王建, 林法伟, 颜蓓蓓, 陈冠益. 基于钙钛矿氧化物的金属纳米粒子溶出策略：溶出过程、驱动力及控制策略[J]. 化工进展, 2023, 42(6): 3049-3065.

Figures/Tables 2

References 95

1	廖丰, 龙明策. 黏土负载型类Fenton催化剂的研究进展[J]. 化工进展, 2018, 37(9): 3401-3409.
	LIAO Feng, LONG Mingce. Recent progress on the clay supported Fenton-like catalyst[J]. Chemical Industry and Engineering Progress, 2018, 37(9): 3401-3409.
2	KIM Seona, Areum JUN, KWON Ohhun, et al. Nanostructured double perovskite cathode with low sintering temperature for intermediate temperature solid oxide fuel cells[J]. ChemSusChem, 2015, 8(18): 3153-3158.
3	SCHLUPP M V, EVANS A, MARTYNCZUK J, et al. Micro-solid oxide fuel cell membranes prepared by aerosol-assisted chemical vapor deposition[J]. Advanced Energy Materials, 2014, 4(5): 1301383.
4	ARANDIA Aitor, REMIRO Aingeru, VALLE Beatriz, et al. Deactivation of Ni spinel derived catalyst during the oxidative steam reforming of raw bio-oil[J]. Fuel, 2020, 276: 117995.
5	OCHOA Aitor, ARAMBURU Borja, VALLE Beatriz, et al. Role of oxygenates and effect of operating conditions in the deactivation of a Ni supported catalyst during the steam reforming of bio-oil[J]. Green Chemistry, 2017, 19(18): 4315-4333.
6	林俊明, 岑洁, 李正甲, 等. Ni基重整催化剂失活机理研究进展[J]. 化工进展, 2022, 41(1): 201-209.
	LIN Junming, CEN Jie, LI Zhengjia, et al. Development on deactivation mechanism of Ni-based reforming catalysts[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 201-209.
7	刘嘉辉, 孙道安, 杜咏梅, 等. 芳烃蒸汽催化重整制氢研究进展[J]. 化工进展, 2021, 40(9): 4782-4790.
	LIU Jiahui, SUN Dao’an, DU Yongmei, et al. Progress on hydrogen production from catalytic steam reforming of aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4782-4790.
8	TANAKA Hirohisa, TAN Isao, UENISHI Mari, et al. Regeneration of palladium subsequent to solid solution and segregation in a perovskite catalyst: an intelligent catalyst[J]. Topics in Catalysis, 2001, 16(1/2/3/4): 63-70.
9	NISHIHATA Y, MIZUKI J, AKAO T, et al. Self-regeneration of a Pd-perovskite catalyst for automotive emissions control[J]. Nature, 2002, 418(6894): 164-167.
10	TANAKA Hirohisa, UENISHI Mari, TANIGUCHI Masashi, et al. Intelligent catalyst having the self-regenerative function of Pd, Rh and Pt for automotive emissions control[J]. Catalysis Today, 2006, 117(1/2/3): 321-328.
11	CUI Shaohua, LI Jianhui, ZHOU Xinwen, et al. Cobalt doped LaSrTiO_3- _δ as an anode catalyst: effect of Co nanoparticle precipitation on SOFCs operating on H₂S-containing hydrogen[J]. Journal of Materials Chemistry A, 2013, 1(34): 9689-9696.
12	HUA Bin, LI Meng, SUN Yifei, et al. Enhancing perovskite electrocatalysis of solid oxide cells through controlled exsolution of nanoparticles[J]. ChemSusChem, 2017, 10(17): 3333-3341.
13	王一帆, 孙毅飞, 盖鑫磊, 等. 纳/微异构型钙钛矿氧化物电极在固体氧化物燃料电池的研究进展[J]. 硅酸盐学报, 2021, 49(01): 70-82.
	WANG Yifan, SUN Yifei, GE Xinlei, et al. Recent development on nano-and micron-heteromorphism perovskite oxide nanofiber electrode for SOFC[J]. Journal of the Chinese Ceramic Society, 2021, 49(1): 70-82.
14	GRABOWSKA Ewelina. Selected perovskite oxides: Characterization, preparation and photocatalytic properties—A review[J]. Applied Catalysis B: Environmental, 2016, 186: 97-126.
15	陈彦广, 闫伟宁, 韩洪晶, 等. 钙钛矿氧化物的制备及其在环境保护中的应用[J]. 硅酸盐通报, 2016, 35(7): 2142-2148.
	CHEN Yanguang, YAN Weining, HAN Hongjing, et al. Preparation of perovskite oxide and its application in environmental protection[J]. Bulletin of the Chinese Ceramic Society, 2016, 35(7): 2142-2148.
16	李翠翠, 张婷, 安静, 等. 三维有序大孔钙钛矿金属氧化物作为高效燃烧催化剂的研究进展[J]. 化工进展, 2021, 40(6): 3181-3190.
	LI Cuicui, ZHANG Ting, AN Jing, et al. Research progress of three-dimensional ordered macroporous perovskite metal oxides as highly efficient combustion catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3181-3190.
17	杨杰, 常辉, 隋志军, 等. 化学链催化甲烷氧化反应研究进展[J]. 化工进展, 2021, 40(4): 1928-1947.
	YANG Jie, CHANG Hui, SUI Zhijun, et al. Advances in chemical looping methane oxidation[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 1928-1947.
18	程雅娣, 高建雄, 王焕磊, 等. 钙钛矿氧化物结构分析及其电催化析氢反应研究进展[J]. 分析化学, 2021, 49(6): 952-962.
	CHENG Yadi, GAO Jianxiong, WANG Huanlei, et al. Structure analysis of perovskite oxides and research progress on their electrocatalytic hydrogen evolution reaction[J]. Chinese Journal of Analytical Chemistry, 2021, 49(6): 952-962.
19	阚家伟, 李兵, 李林, 等. 含氯挥发性有机化合物催化燃烧催化剂的研究进展[J]. 化工进展, 2016, 35(2): 499-505.
	KAN Jiawei, LI Bing, LI Lin, et al. Advances in catalysts for catalytic combustion of chlorinated volatile organic compounds[J]. Chemical Industry and Engineering Progress, 2016, 35(2): 499-505.
20	CAO T, KWON O, GORTE R J, et al. Metal exsolution to enhance the catalytic activity of electrodes in solid oxide fuel cells[J]. Nanomaterials, 2020, 10(12): 2445.
21	KATZ M B, ZHANG S, DUAN Y, et al. Reversible precipitation/dissolution of precious-metal clusters in perovskite-based catalyst materials: Bulk versus surface re-dispersion[J]. Journal of Cataltsis, 2012, 293: 145-148.
22	RAMAN A S, VOJVODIC A. Modeling exsolution of Pt from ATiO₃ perovskites (A=Ca/Sr/Ba) using first-principles methods[J]. Chemistry of Materials, 2020, 32(22): 9642-9649.
23	OH T S, RAHANI E K, NEAGU D, et al. Evidence and model for strain-driven release of metal nanocatalysts from perovskites during exsolution[J]. Journal of Physical Chemistry Letters, 2015, 6(24): 5106-5110.
24	GAO Yang, CHEN Dengjie, SACCOCCIO Mattia, et al. From material design to mechanism study: Nanoscale Ni exsolution on a highly active A-site deficient anode material for solid oxide fuel cells[J]. Nano Energy, 2016, 27: 499-508.
25	NEAGU D, KYRIAKOU V, ROIBAN I L, et al. In situ observation of nanoparticle exsolution from perovskite oxides: From atomic scale mechanistic insight to nanostructure tailoring[J]. ACS Nano, 2019, 13(11): 12996-13005.
26	KWON Ohhun, KIM Kyeounghak, Sangwook JOO, et al. Self-assembled alloy nanoparticles in a layered double perovskite as a fuel oxidation catalyst for solid oxide fuel cells[J]. Journal of Materials Chemistry A, 2018, 6(33): 15947-15953.
27	NEAGU D, OH T S, MILLER D N, et al. Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution[J]. Nature Communications, 2015, 6: 8120.
28	TANAKA Hirohisa, TANIGUCHI Masashi, UENISHI Mari, et al. Self-regenerating Rh- and Pt-based perovskite catalysts for automotive-emissions control[J]. Angewandte Chemie International Edition, 2006, 45(36): 5998-6002.
29	DU Zhihong, GONG Yue, ZHAO Hailei, et al. Unveiling the interface structure of the exsolved Co-Fe alloy nanoparticles from double perovskite and its application in solid oxide fuel cells[J]. ACS Applied Materials & Interfaces, 2021, 13(2): 3287-3294.
30	ZHANG Yuxuan, YU Zhouyang, TAO Youkun, et al. Insight into the electrochemical processes of the titanate electrode with in situ Ni exsolution for solid oxide cells[J]. ACS Applied Energy Materials, 2019, 2(6): 4033-4044.
31	Houfu LYU, LIU Tianfu, ZHANG Xiaomin, et al. Atomic-scale insight into exsolution of CoFe alloy nanoparticles in La_0.4Sr_0.6Co_0.2Fe_0.7Mo_0.1O_3- _δ with efficient CO₂ electrolysis[J]. Angewandte Chemie-International Edition, 2020, 59(37): 15968-15973.
32	SONG Yufei, WANG Wei, GE Lei, et al. Rational design of a water-storable hierarchical architecture decorated with amorphous barium oxide and nickel nanoparticles as a solid oxide fuel cell anode with excellent sulfur tolerance[J]. Advanced Science, 2017, 4(11): 1700337.
33	SUN Yifei, LI Jianhui, CUI Lin, et al. A-site-deficiency facilitated in situ growth of bimetallic Ni-Fe nano-alloys: A novel coking-tolerant fuel cell anode catalyst[J]. Nanoscale, 2015, 7(25): 11173-11181.
34	UENISHI Mari, TANIGUCHI Masashi, TANAKA Hirohisa, et al. Redox behavior of palladium at start-up in the perovskite-type LaFePdO _x automotive catalysts showing a self-regenerative function[J]. Applied Catalysis B: Environmental, 2005, 57(4): 267-273.
35	Houfu LYU, LIN Le, ZHANG Xiaomin, et al. In situ investigation of reversible exsolution/dissolution of CoFe alloy nanoparticles in a Co-doped Sr₂Fe_1.5Mo_0.5O_6- _δ cathode for CO₂ electrolysis[J]. Advanced Materials, 2020, 32(6): 1906193.
36	LINDENTHAL Lorenz, POPOVIC Janko, RAMESHAN Raffael, et al. Novel perovskite catalysts for CO₂ utilization-exsolution enhanced reverse water-gas shift activity[J]. Applied Catalysis B-Environmental, 2021, 292: 120183.
37	WANG Haiqian, DONG Xiaolei, ZHAO Tingting, et al. Dry reforming of methane over bimetallic Ni-Co catalyst prepared from La(Co _x Ni_1- _x )_0.5Fe_0.5O₃ perovskite precursor: Catalytic activity and coking resistance[J]. Applied Catalysis B: Environmental, 2019, 245: 302-313.
38	DEKA D J, KIM J, GUNDUZ S, et al. Investigation of hetero-phases grown via in-situ exsolution on a Ni-doped (La,Sr)FeO₃ cathode and the resultant activity enhancement in CO₂ reduction[J]. Applied Catalysis B: Environmental, 2021, 286: 119917.
39	GOTSCH T, SCHLICKER L, BEKHEET M F, et al. Structural investigations of La_0.6Sr_0.4FeO_3- _δ under reducing conditions: Kinetic and thermodynamic limitations for phase transformations and iron exsolution phenomena[J]. RSC Advances, 2018, 8(6): 3120-3131.
40	HAMADA Ikutaro, UOZUMI Akifumi, MORIKAWA Yoshitada, et al. A density functional theory study of self-regenerating catalysts LaFe_1- _x M _x O_3- _y (M=Pd, Rh, Pt)[J]. Journal of the American Chemical Society, 2011, 133(46): 18506-18509.
41	TIAN Zhixue, UOZUMI Akifumi, HAMADA Ikutaro, et al. First-principles investigation on the segregation of Pd at LaFe_1- _x Pd _x O_3- _y surfaces[J]. Nanoscale Research Letters, 2013, 8: 203.
42	KWON Ohhun, SENGODAN Sivaprakash, KIM Kyeounghak, et al. Exsolution trends and co-segregation aspects of self-grown catalyst nanoparticles in perovskites[J]. Nature Communications, 2017, 8: 15967.
43	YANG Chenghao, YANG Zhibin, JIN Chao, et al. Sulfur-tolerant redox-reversible anode material for direct hydrocarbon solid oxide fuel cells[J]. Advanced Materials, 2012, 24(11): 1439-1443.
44	DU Zhihong, ZHAO Hailei, YI Sha, et al. High-performance anode material Sr₂FeMo_0.65Ni_0.35O_6- _δ with in situ exsolved nanoparticle catalyst[J]. ACS Nano, 2016, 10(9): 8660-8669.
45	SENGODAN Sivaprakash, CHOI Sihyuk, Areum JUN, et al. Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells[J]. Nature Materials, 2015, 14(2): 205-209.
46	SUN Yifei, ZHANG Yaqian, CHEN Jian, et al. New opportunity for in situ exsolution of metallic nanoparticles on perovskite parent[J]. Nano Letters, 2016, 16(8): 5303-5309.
47	WEBER M L, WILHELM M, JIN L, et al. Exsolution of embedded nanoparticles in defect engineered perovskite layers[J]. ACS Nano, 2021, 15(3): 4546-4560.
48	SUN Xiang, CHEN Huijun, YIN Yimei, et al. Progress of exsolved metal nanoparticles on oxides as high performance (electro)catalysts for the conversion of small molecules[J]. Small, 2021, 17(10): 2005383.
49	ZHANG Jiawei, GAO Minrui, LUO Jingli. In situ exsolved metal nanoparticles: A smart approach for optimization of catalysts[J]. Chemistry of Materials, 2020, 32(13): 5424-5241.
50	GUI Liangqi, PAN Guohong, MA Xing, et al. In-situ exsolution of CoNi alloy nanoparticles on LiFe_0.8Co_0.1Ni_0.1O₂ parent: New opportunity for boosting oxygen evolution and reduction reaction[J]. Applied Surface Science, 2021, 543: 148817.
51	Sangwook JOO, SEONG Arim, KWON Ohhun, et al. Highly active dry methane reforming catalysts with boosted in situ grown Ni-Fe nanoparticles on perovskite via atomic layer deposition[J]. Science Advances, 2020, 6(35): eabb1573.
52	NEAGU D, TSEKOURAS G, MILLER D N, et al. In situ growth of nanoparticles through control of non-stoichiometry[J]. Nature Chemistry, 2013, 5(11): 916-923.
53	Sangwook JOO, KWON Ohhun, KIM Kyeounghak, et al. Cation-swapped homogeneous nanoparticles in perovskite oxides for high power density[J]. Nature Communications, 2019, 10: 697.
54	WANG J, YANG J, OPITZ A K, et al. Tuning point defects by elastic strain modulates nanoparticle exsolution on perovskite oxides[J]. Chemistry of Materials, 2021, 33(13): 5021-5034.
55	LEE W, HAN J W, CHEN Y, et al. Cation size mismatch and charge interactions drive dopant segregation at the surfaces of manganite perovskites[J]. Journal of American Chemical Society, 2013, 135(21): 7909-7925.
56	NEAGU D, IRVINE J T. Structure and properties of La_0.4Sr_0.4TiO₃ ceramics for use as anode materials in solid oxide fuel cells[J]. Chemistry of Materials, 2010, 22(17): 5042-5053.
57	FAN Weiwei, SUN Zhu, BAI Yu, et al. In situ growth of nanoparticles in A-site deficient ferrite perovskite as an advanced electrode for symmetrical solid oxide fuel cells[J]. Journal of Power Sources, 2020, 456: 228000.
58	GAO Y, LU Z, YOU T L, et al. Energetics of nanoparticle exsolution from perovskite oxides[J]. Journal of Physical Chemistry Letters, 2018, 9(13): 3772-3778.
59	WU Yujie, WANG Shuai, GAO Yue, et al. In situ growth of copper-iron bimetallic nanoparticles in A-site deficient Sr₂Fe_1.5Mo_0.5O_6- _δ as an active anode material for solid oxide fuel cells[J]. Journal of Alloys and Compounds, 2022, 926: 166852.
60	GUO Jia, CAI Rongsheng, CALI Eleonora, et al. Low-temperature exsolution of Ni-Ru bimetallic nanoparticles from A-site deficient double perovskites[J]. Small, 2022, 18(43): 2107020.
61	MANAGUTTI P B, TYMEN S, LIU X, et al. Exsolution of Ni nanoparticles from A-site-deficient layered double perovskites for dry reforming of methane and as an anode material for a solid oxide fuel cell[J]. Acs Applied Materials & Interfaces, 2021, 13(30): 35719-35728.
62	CONG Yingge, GENG Zhibin, SUN Yu, et al. Cation segregation of A-site deficiency perovskite La_0.85FeO_3- _δ nanoparticles toward high-performance cathode catalysts for rechargeable LiO₂ battery[J]. Acs Applied Materials & Interfaces, 2018, 10(30): 25465-25472.
63	TSEKOURAS G, NEAGU D, IRVINE J T. Step-change in high temperature steam electrolysis performance of perovskite oxide cathodes with exsolution of B-site dopants[J]. Energy & Environmental Science, 2013, 6(1): 256-266.
64	Houfu LYU, LIN Le, ZHANG Xiaomin, et al. Promoting exsolution of RuFe alloy nanoparticles on Sr₂Fe_1.4Ru_0.1Mo_0.5O_6- _δ via repeated redox manipulations for CO₂ electrolysis[J]. Nature Communications, 2021, 12(1): 5665.
65	NEAGU D, PAPAIOANNOU E I, RAMLI W K, et al. Demonstration of chemistry at a point through restructuring and catalytic activation at anchored nanoparticles[J]. Nature Communications, 2017, 8: 1855.
66	TANG Chenyang, KOUSI Kalliopi, NEAGU Dragos, et al. Towards efficient use of noble metals via exsolution exemplified for CO oxidation[J]. Nanoscale, 2019, 11(36): 16935-16944.
67	HAN H, PARK J, NAM S Y, et al. Lattice strain-enhanced exsolution of nanoparticles in thin films[J]. Nature Communitions, 2019, 10: 1471.
68	KIM J K, JO Y R, KIM S, et al. Exceptional tunability over size and density of spontaneously formed nanoparticles via nucleation dynamics[J]. Acs Applied Materials & Interfaces, 2020, 12(21): 24039-24047.
69	MYUNG J H, NEAGU D, MILLER D N, et al. Switching on electrocatalytic activity in solid oxide cells[J]. Nature, 2016, 537(7621): 528-531.
70	KHALID Hessan, Atta UL HAQ, ALESSI Bruno, et al. Rapid plasma exsolution from an A-site deficient perovskite oxide at room temperature[J]. Advanced Energy Materials, 2022， 12（45）： 2201131.
71	LAI K Y, MANTHIRAM A. Evolution of exsolved nanoparticles on a perovskite oxide surface during a redox process[J]. Chem Mater, 2018, 30(8): 2838-2847.
72	MA Jiaojiao, GENG Zhibin, JIANG Yilan, et al. Exsolution manipulated local surface cobalt/iron alloying and dealloying conversion in La_0.95Fe_0.8Co_0.2O₃ perovskite for oxygen evolution reaction[J]. Journal of Alloys and Compounds, 2021, 854: 157154.
73	DIMITRAKOPOULOS G, GHONIEM A F, YILDIZ B. In situ catalyst exsolution on perovskite oxides for the production of CO and synthesis gas in ceramic membrane reactors[J]. Sustainable Energy & Fuels, 2019, 3(9): 2347-2355.
74	QIAO Sifan, QI Jingang, ZHANG Di, et al. Pulsed electric current boosts electrochemical performance and electro-conductivity of La _x Sr_1- _x Cr _y Ni_1- _y O₃ perovskite via exsolution of nanoparticles[J]. Nanotechnology, 2019, 30(42): 425301.
75	许爱晨, 商剑, 乔思凡, 等. 脉冲电流促进(La, Sr)(Ti, Ni)O₃原位溶出金属纳米颗粒的研究[J]. 功能材料, 2020, 51(10): 10100-10104.
	XU Aichen, SHANG Jian, QIAO Sifan, et al. Study on the metal particles exsolutionin situ of (La,Sr)(Ti,Ni)O₃ perovskite oxides via pulsed electric current technology[J]. Journal of Functional Materials, 2020, 51(10): 10100-10104.
76	KYRIAKOU V, SHARMA R K, NEAGU D, et al. Plasma driven exsolution for nanoscale functionalization of perovskite oxides[J]. Small Methods, 2021, 5(12): 2100868.
77	WEI Tong, JIA Lichao, ZHENG Haoyu, et al. LaMnO₃-based perovskite with in-situ exsolved Ni nanoparticles: a highly active, performance stable and coking resistant catalyst for CO₂ dry reforming of CH₄ [J]. Applied Catalysis A: General, 2018, 564: 199-207.
78	OH J, JOO S, LIM C, et al. Precise modulation of triple-phase boundaries towards a highly functional exsolved catalyst for dry reforming of methane under a dilution-free system[J]. Angewandte Chemie International Edition, 2022, 61(33): e202204990.
79	杨晓幸, 苗鹤, 袁金良. 可逆固体氧化物燃料电池氧电极材料的研究进展[J]. 化工进展, 2021, 40(9): 4904-4917.
	YANG Xiaoxing, MIAO He, YUAN Jinliang. Research progress on oxygen electrode materials for reversible solid oxide fuel cells[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4904-4917.
80	Sebastian VECINO-MANTILLA, Paola GAUTHIER-MARADEI, HUVE Marielle, et al. Nickel exsolution-driven phase transformation from an n=2 to an n=1 Ruddlesden-Popper manganite for methane steam reforming reaction in SOFC conditions[J]. ChemCatChem, 2019, 11(18): 4631-4641.
81	WANG Yao, LIU Tong, LI Mei, et al. Exsolved Fe-Ni nano-particles from Sr₂Fe_1.3Ni_0.2Mo_0.5O₆ perovskite oxide as a cathode for solid oxide steam electrolysis cells[J]. Journal of Materials Chemistry A, 2016, 4(37): 14163-14169.
82	QIN Mingxia, XIAO Yu, YANG Hongyu, et al. Ru/Nb co-doped perovskite anode: Achieving good coking resistance in hydrocarbon fuels via core-shell nanocatalysts exsolution[J]. Applied Catalysis B-Environmental, 2021, 299: 120613.
83	JIANG Yilan, GENG Zhibin, YUAN Long, et al. Nanoscale architecture of RuO₂/La_0.9Fe_0.92Ru_0.08- _x O_3- _δ composite via manipulating the exsolution of low Ru-substituted A-site deficient perovskite[J]. Acs Sustainable Chemistry & Engineering, 2018, 6(9): 11999-12005.
84	WANG Yarong, WANG Zhangjun, JIN Chao, et al. Enhanced overall water electrolysis on a bifunctional perovskite oxide through interfacial engineering[J]. Electrochimica Acta, 2019, 318: 120-129.
85	SUN Yifei, ZHANG Yaqian, YANG Yanling, et al. Smart tuning of 3D ordered electrocatalysts for enhanced oxygen reduction reaction[J]. Applied Catalysis B: Environmental, 2017, 219: 640-644.
86	SUN Yifei, YANG Yanling, CHEN Jian, et al. Toward a rational photocatalyst design: A new formation strategy of co-catalyst/semiconductor heterostructures via in situ exsolution[J]. Chemical Communications, 2018, 54(12): 1505-1508.
87	XU X, LIU G, AZAD A K. Visible light photocatalysis by in situ growth of plasmonic Ag nanoparticles upon AgTaO₃ [J]. International Journal of Hydrogen Energy, 2015, 40(9): 3672-3678.
88	OH J H, KWON B W, CHO J, et al. Importance of exsolution in transition-metal (Co, Rh, and Ir)-doped LaCrO₃ perovskite catalysts for boosting dry reforming of CH₄ using CO₂ for hydrogen production[J]. Industrial Engineering Chemistry Research, 2019, 58(16): 6385-6393.
89	JOO S, KIM K, KWON O, et al. Enhancing thermocatalytic activities by upshifting the d-band center of exsolved Co-Ni-Fe ternary alloy nanoparticles for the dry reforming of methane[J]. Angewandte Chemie International Edition, 2021, 60(29): 15912-15919.
90	YE Lingting, ZHANG Minyi, HUANG Ping, et al. Enhancing CO₂ electrolysis through synergistic control of non-stoichiometry and doping to tune cathode surface structures[J]. Nature Communications, 2017, 8: 14785.
91	PARK Seongmin, KIM Yoongon, HAN Hyunsu, et al. In situ exsolved Co nanoparticles on Ruddlesden-Popper material as highly active catalyst for CO₂ electrolysis to CO[J]. Applied Catalysis B: Environmental, 2019, 248: 147-156.
92	YANG Liming, XIE Kui, XU Shanshan, et al. Redox-reversible niobium-doped strontium titanate decorated with in situ grown nickel nanocatalyst for high-temperature direct steam electrolysis[J]. Dalton Transactions, 2014, 43(37): 14147-14157.
93	KYRIAKOU Vasileios, NEAGU Dragos, PAPAIOANNOU Evangelos I, et al. Co-electrolysis of H₂O and CO₂ on exsolved Ni nanoparticles for efficient syngas generation at controllable H₂/CO ratios[J]. Applied Catalysis B: Environmental, 2019, 258: 117950.
94	YANG C H, YANG Z B, JIN C, et al. High performance solid oxide electrolysis cells using Pr_0.8Sr_1.2(Co,Fe)_0.8Nb_0.2O₄₊ _δ -Co-Fe alloy hydrogen electrodes[J]. International Journal of Hydrogen Energy, 2013, 38(26): 11202-11208.
95	LI Qinghao, ZHOU Jun, FU Lei, et al. Fabrication of heterostructural Ru-SrTiO₃ fibers through in-situ exsolution for visible-light-induced photocatalysis [J]. Journal of Alloys and Compounds, 2022, 925: 166747.

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