Controlled Synthesis of Noble Metal Aerogels and Their Applications in Electrocatalysis and Surface-Enhanced Raman Scattering

doi:10.6023/A24030108

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (7): 805-818.DOI: 10.6023/A24030108 Previous Articles Next Articles

Account

贵金属气凝胶的可控制备及其电催化与表面增强拉曼散射应用

李一^a, 翁蓓蓓^a, 赵静雯^a, 杜然^a^,^b^,^*()

a 北京理工大学材料学院北京 100081
b 北京理工大学唐山研究院唐山 063000

投稿日期:2024-03-31 发布日期:2024-05-13

作者简介:

杜然, 北京理工大学教授. 2016年毕业于北京大学, 获得物理化学博士学位, 随后先后赴新加坡南洋理工大学、德国德累斯顿工业大学、香港大学等地从事博士后研究. 2021年加盟北京理工大学. 先后获得北京大学优秀博士论文、德国洪堡学者、USERN Prize提名(物理与化学科学领域)等荣誉, 入选2020年度海外高层次人才引进计划青年项目, 任SmartMat、National Science Open青年编委. 主要研究领域为以金属气凝胶为代表的先进气凝胶的可控制备及其在电催化、环境治理、智能材料等领域的应用.

基金资助:
北京市自然科学基金(2232063); 国家自然科学基金(22202009); 大学生创新创业训练项目(BIT2023LH083); 北京理工大学研究生科研水平和创新能力提升专项计划(2023YCXY040)

Controlled Synthesis of Noble Metal Aerogels and Their Applications in Electrocatalysis and Surface-Enhanced Raman Scattering

Yi Li^a, Beibei Weng^a, Jingwen Zhao^a, Ran Du^a^,^b^,^*()

a School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
b Tangshan Research Institute, Beijing Institute of Technology, Tangshan 063000, China

Received:2024-03-31 Published:2024-05-13
Contact: *E-mail: rdu@bit.edu.cn
Supported by:
Beijing Natural Science Foundation(2232063); National Natural Science Foundation of China(22202009); College Students’ Innovation and Entrepreneurship Training Program(BIT2023LH083); BIT Research and Innovation Promoting Project(2023YCXY040)

Noble metal aerogels (NMAs) are an emerging class of porous materials that are entirely constructed by one or more kinds of nanostructured noble metals including gold (Au), silver (Ag), palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), osmium (Os), and iridium (Ir). They feature attributes of both nanostructured noble metals (e.g., high catalytic activity, high electrical conductivity, and special optical properties) and aerogels (e.g., self-standing architecture, large specific surface area, abundant pores, and robust 3D networked structure). Therefore, since their discovery in 2009, NMAs have displayed tremendous potential in fields ranging from (electro)catalysis, battery electrodes, biosensing, plasmonic technologies, and environment remediation. However, as young materials, the investigation of NMAs is far from sufficient. Controlled synthesis is the basis for new materials that dictate how far they can reach. The sol-gel behavior of the metal system is distinct from that of conventional gel systems, thus requiring additional studies. However, the fundamental understanding of the fabrication process and thus the structure/composition control for NMAs are largely overlooked. In this context, our team has been focusing on developing effective fabrication strategies based on an in-depth understanding of the gelation mechanisms as well as the roles played by each component in the reaction. To this end, we have pioneered realizing ligament size control, unveiling the reductant chemistry, unlocking the ligand chemistry, and achieving minute-scale rapid gelation by counter-intuitionally introducing force fields. We aim to eventually realize arbitrary manipulation of the composition and structure of NMAs, which is critical for paving the way for their further development. After gaining sufficient control capacity for NMAs, then we go for exploring their applications. It is crucial to select appropriate scenarios according to their unique attributes, so as to fully exert their potential and eventually find their disruptive application directions. Inheriting features of noble metals and aerogels, NMAs possess abundant catalytic/optical active sites, high electronic/mass transfer channels, and robust and self-supported networks. In this regard, they should be suited for the (photo)electrocatalysis and detection based on surface-enhanced Raman scattering (SERS). Indeed, numerous studies have demonstrated their exceptional electrocatalytic performances towards diverse reactions such as the alcohol oxidation reaction (AOR), hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and carbon dioxide reduction reaction (CO₂RR). We further pioneered incorporating light in the electrocatalytic process, opening the photoelectrocatalysis direction. Additionally, we found that Au aerogels can serve as ideal 3D SERS substrates for they feature hot spots across three dimensions, which enables their outstanding signal enhancement and misfocus tolerance. However, intentionally on-target performance optimi-zation and the exploration of new design perspectives for NMAs are still on the way. In this account, we summarize the representative endeavors made in controlled synthesis and electrocatalysis/SERS applications of NMAs. After a brief introduction of NMAs, we will highlight the state-of-the-art understanding of the sol-gel process of metal systems, and how to achieve structure-controlled synthesis and rapid fabrication of NMAs. After narrating the progress in electrocatalysis and SERS applications, we will conclude the challenges and opportunities for these young materials.

Key words: aerogels, sol-gel, nanostructures, electrocatalysis, surface-enhanced Raman scattering

Cite this article

Yi Li, Beibei Weng, Jingwen Zhao, Ran Du. Controlled Synthesis of Noble Metal Aerogels and Their Applications in Electrocatalysis and Surface-Enhanced Raman Scattering[J]. Acta Chimica Sinica, 2024, 82(7): 805-818.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 12

Figure 1. Au aerogels before and after compression[4]

Figure 2. The gravity-driven sol-gel behavior of the Au system. (A, B) The fabrication process of the Au aerogels. (C) The UV-vis spectra of the reaction systems recorded at different heights. (D, E) Time-lapse dynamic light scattering and optical microscopy of the sol-gel process[4]

Figure 3. Self-healing properties of Au hydrogels[4]

Figure 4. Modulation of the ligament size for Au aerogels. (A, B) Au aerogels prepared by using different salts[4]. (C, D) Mechanisms for synthesizing Au aerogels by applying excessive sodium borohydride and the ligament sizes by including different ligands during synthesis[11]. (E, F) Fabrication of ultrafine Au aerogels by assembling Au nanoclusters, (E) Au nanoclusters, and (F) Au aerogels[25]

Figure 5. Dimensional modulation of the building blocks of noble metal aerogels. The dimension of the building blocks of Pt-Bi aerogels can be manipulated by adjusting the composition and the ligands[15]

Figure 6. Hierarchical structure control of noble metal aerogels. Synthesis of (A, B) Au aerogels via a freeze-thaw method[14] and (C, D) Ni aerogels via a magnetic field-assisted method[34]

Figure 7. Element distribution modulation of noble metal aerogels. (A~C) Au-Pd core-shell aerogels and their preparation process[13]. (D) Au-Pt and Au-Pd-Pt core-shell aerogels[4]

Figure 8. The disturbance-directed rapid fabrication of noble metal aerogels. (A) Fabrication process and (B, C) diverse obtained aerogels[9]

Figure 9. Application of noble metal aerogels for electrocatalysis. (A) Polarization curves of noble metal aerogels for hydrogen evolution, and (B) water-splitting performances with Au-Rh aerogel-based hydrogen evolution electrocatalysts under different pH values[12]. (C) Cu@Fe@Ni core-shell aerogels for electrocatalytic oxygen evolution[46]

Figure 10. Application of noble metal aerogels for photoelectrocatalysis. (A) The CV curves of the electrocatalytic ethanol oxidation process in dark and (B) the plot of mass activity versus light power density[14]

Figure 11. Application of noble metal aerogels for surface-enhanced Raman scattering. (A, B) The Raman enhancement factors of R6G with Au aerogels of different ligament sizes as substrates excited by different laser wavelengths. (C) Raman spectra of R6G recorded on different substrates. (D, E) Raman spectra of R6G recorded on 8 nm Au film and Au aerogels at different defocuses[16]

Figure 12. Research directions for NMAs

References 53

[1]	Wittstock G.; Bäumer M.; Dononelli W.; Klüner T.; Lührs L.; Mahr C.; Moskaleva L. V.; Oezaslan M.; Risse T.; Rosenauer A.; Staubitz A.; Weissmüller J.; Wittstock A. Chem. Rev. 2023, 123, 6716. doi: 10.1021/acs.chemrev.2c00751 pmid: 37133401
[2]	Kistler S. S. Nature 1931, 127, 741.
[3]	Bigall N. C.; Herrmann A. K.; Vogel M.; Rose M.; Simon P.; Carrillo-Cabrera W.; Dorfs D.; Kaskel S.; Gaponik N.; Eychmuller A. Angew. Chem. Int. Ed. 2009, 48, 9731. doi: 10.1002/anie.200902543 pmid: 19918827
[4]	Du R.; Hu Y.; Hübner R.; Joswig J.-O.; Fan X.; Eychmüller A. Sci. Adv. 2019, 5, eaaw4590.
[5]	Wang N.; Li Y.; Cui Q.; Sun X.; Hu Y.; Luo Y.; Du R. Acta Phys.-Chim. Sin. 2023, 39, 2212014 (in Chinese).
	(王宁, 李一, 崔乾, 孙晓玥, 胡悦, 罗运军, 杜然, 物理化学学报, 2023, 39, 2212014.)
[6]	Du R.; Eychmüller A. Catalysts 2023, 13, 1451.
[7]	Jiang X.; Du R.; Hübner R.; Hu Y.; Eychmüller A. Matter 2021, 4, 54.
[8]	Du R.; Fan X.; Jin X.; Hübner R.; Hu Y.; Eychmüller A. Matter 2019, 1, 39.
[9]	Du R.; Joswig J.-O.; Fan X.; Hübner R.; Spittel D.; Hu Y.; Eychmüller A. Matter 2020, 2, 908.
[10]	Fan X.; Zerebecki S.; Du R.; Hübner R.; Marzum G.; Jiang G.; Hu Y.; Barcikowki S.; Reichenberger S.; Eychmüller A. Angew. Chem. Int. Ed. 2020, 59, 5706.
[11]	Du R.; Wang J.; Wang Y.; Hübner R.; Fan X.; Senkovska I.; Hu Y.; Kaskel S.; Eychmüller A. Nat. Commun. 2020, 11, 1590.
[12]	Du R.; Jin W.; Hübner R.; Zhou L.; Hu Y.; Eychmüller A. Adv. Energy Mater. 2020, 10, 1903857.
[13]	Du R.; Jin W.; Wu H.; Hübner R.; Zhou L.; Xue G.; Hu Y.; Eychmüller A. J. Mater. Chem. A 2021, 9, 17189.
[14]	Du R.; Joswig J.-O.; Hübner R.; Zhou L.; Wei W.; Hu Y.; Eychmüller A. Angew. Chem. Int. Ed. 2020, 59, 8293.
[15]	Xue G.; Li Y.; Du R.; Wang J.; Hübner R.; Gao M.; Hu Y. Small 2023, 19, 2301288.
[16]	Zhou L.; Peng Y.; Zhang N.; Du R.; Hübner R.; Wen X.; Li D.; Hu Y.; Eychmüller A. Adv. Opt. Mat. 2021, 9, 2100352.
[17]	Du R.; Jin X.; Hübner R.; Fan X.; Hu Y.; Eychmüller A. Adv. Energy Mater. 2020, 10, 1901945.
[18]	Tappan B. C.; Steiner S. A.; Luther E. P. Angew. Chem. Int. Ed. 2010, 49, 4544. doi: 10.1002/anie.200902994 pmid: 20514651
[19]	Liu W.; Herrmann A.-K.; Bigall N. C.; Rodriguez P.; Wen D.; Oezaslan M.; Schmidt T. J.; Gaponik N.; Eychmüller A. Acc. Chem. Res. 2015, 48, 154.
[20]	Matter F.; Luna A. L.; Niederberger M. Nano Today 2020, 30, 100827.
[21]	Ranmohotti K. G. S.; Gao X.; Arachchige I. U. Chem. Mater. 2013, 25, 3528.
[22]	Zhu C.; Shi Q.; Fu S.; Song J.; Xia H.; Du D.; Lin Y. Adv. Mater. 2016, 28, 8779.
[23]	Zhang H.; Wang D. Angew. Chem. Int. Ed. 2008, 47, 3984. doi: 10.1002/anie.200705537 pmid: 18404751
[24]	Zaccarelli E. J. Phys.: Condens. Matter 2007, 19, 323101.
[25]	Xu J.; Sun F.; Li Q.; Yuan H.; Ma F.; Wen D.; Shang L. Small 2022, 18, 2200525.
[26]	Wen D.; Liu W.; Haubold D.; Zhu C.; Oschatz M.; Holzschuh M.; Wolf A.; Simon F.; Kaskel S.; Eychmüller A. ACS Nano 2016, 10, 2559.
[27]	Du R.; Gao X.; Feng Q.; Zhao Q.; Li P.; Deng S.; Shi L.; Zhang J. Adv. Mater. 2016, 28, 936.
[28]	Yazdan-Abad M. Z.; Noroozifar M.; Modaresi Alam A. R.; Saravani H. J. Mater. Chem. A 2017, 5, 10244.
[29]	Zareie Yazdan-Abad M.; Noroozifar M.; Douk A. S.; Modarresi-Alam A. R.; Saravani H. Appl. Catal., B-Environ. 2019, 250, 242. doi: 10.1016/j.apcatb.2019.02.064
[30]	Cai B.; Wen D.; Liu W.; Herrmann A. K.; Benad A.; Eychmuller A. Angew. Chem. Int. Ed. 2015, 54, 13101.
[31]	Tang Y.; Yeo K. L.; Chen Y.; Yap L. W.; Xiong W.; Cheng W. J. Mater. Chem. A 2013, 1, 6723.
[32]	Gao H.-L.; Xu L.; Long F.; Pan Z.; Du Y.-X.; Lu Y.; Ge J.; Yu S.-H. Angew. Chem. Int. Ed. 2014, 53, 4561.
[33]	Freytag A.; Sánchez‐Paradinas S.; Naskar S.; Wendt N.; Colombo M.; Pugliese G.; Poppe J.; Demirci C.; Kretschmer I.; Bahnemann D. W.; Behrens P.; Bigall N. C. Angew. Chem. Int. Ed. 2016, 55, 1200. doi: 10.1002/anie.201508972 pmid: 26638874
[34]	Pan W.; Liang C.; Sui Y.; Wang J.; Liu P.; Zou P.; Guo Z.; Wang F.; Ren X.; Yang C. Adv. Funct. Mater. 2022, 32, 2204166.
[35]	Wang J.; Liang C.; Ma X.; Liu P.; Pan W.; Zhu H.; Guo Z.; Sui Y.; Liu H.; Liu L.; Yang C. Adv. Mater. 2024, 36, 2307925.
[36]	Liu W.; Haubold D.; Rutkowski B.; Oschatz M.; Hübner R.; Werheid M.; Ziegler C.; Sonntag L.; Liu S.; Zheng Z.; Herrmann A.-K.; Geiger D.; Terlan B.; Gemming T.; Borchardt L.; Kaskel S.; Czyrska-Filemonowicz A.; Eychmüller A. Chem. Mater. 2016, 28, 6477.
[37]	Li L.; Gao W.; Ye J.; Fan H.; Wen D. J. Mater. Chem. A 2023, 11, 5359.
[38]	Kühn L.; Herrmann A. K.; Rutkowski B.; Oezaslan M.; Nachtegaal M.; Klose M.; Giebeler L.; Gaponik N.; Eckert J.; Schmidt T. J. Chem. Eur. J. 2016, 22, 13446.
[39]	Cai B.; Hübner R.; Sasaki K.; Zhang Y.; Su D.; Ziegler C.; Vukmirovic M. B.; Rellinghaus B.; Adzic R. R.; Eychmüller A. Angew. Chem. Int. Ed. 2018, 57, 2963.
[40]	Liu W.; Rodriguez P.; Borchardt L.; Foelske A.; Yuan J.; Herrmann A. K.; Geiger D.; Zheng Z.; Kaskel S.; Gaponik N.; Kotz R.; Schmidt T. J.; Eychmuller A. Angew. Chem. Int. Ed. 2013, 52, 9849.
[41]	Burpo F. J.; Nagelli E. A.; Morris L. A.; McClure J. P.; Ryu M. Y.; Palmer J. L. J. Mater. Res. 2017, 32, 4153.
[42]	Li W.; Weng B.; Sun X.; Cai B.; Hübner R.; Luo Y.; Du R. Catalysts 2023, 13, 167.
[43]	Liu W.; Herrmann A. K.; Geiger D.; Borchardt L.; Simon F.; Kaskel S.; Gaponik N.; Eychmuller A. Angew. Chem. Int. Ed. 2012, 51, 5743.
[44]	Li H.; Huang H.; Chen Y.; Lai F.; Fu H.; Zhang L.; Zhang N.; Bai S.; Liu T. Adv. Mater. 2023, 35, 2209242.
[45]	Huang H.; Chen C.; Chang C.-C.; Lai F.; Liu S.; Fu H.; Chen Y.; Li H.; Huang W.-H.; Zhang N.; Liu T. Adv. Mater. 2024, 2314142.
[46]	Jiang B.; Wan Z.; Kang Y.; Guo Y.; Henzie J.; Na J.; Li H.; Wang S.; Bando Y.; Sakka Y.; Yamauchi Y. Nano Energy 2021, 81, 105644.
[47]	Wang J.; Chen F.; Jin Y.; Guo L.; Gong X.; Wang X.; Johnston R. L. Nanoscale 2019, 11, 14174.
[48]	Wang H.; Zheng H.; Ling L.; Fang Q.; Jiao L.; Zheng L.; Qin Y.; Luo Z.; Gu W.; Song W.; Zhu C. ACS Nano 2022, 16, 21266.
[49]	Zhang Z.; Zhang C.; Zheng H.; Xu H. Acc. Chem. Res. 2019, 52, 2506.
[50]	Phan-Quang G. C.; Han X.; Koh C. S. L.; Sim H. Y. F.; Lay C. L.; Leong S. X.; Lee Y. H.; Pazos-Perez N.; Alvarez-Puebla R. A.; Ling X. Y. Acc. Chem. Res. 2019, 52, 1844.
[51]	Gao X.; Esteves R. J. A.; Nahar L.; Nowaczyk J.; Arachchige I. U. ACS Appl. Mater. Interfaces 2016, 8, 13076.
[52]	Xiao Y.; Wang C.; Liu K.; Wei L.; Luo Z.; Zeng M.; Yi Y. J. Sol-Gel Sci. Technol. 2021, 99, 614.
[53]	Duan W.; Zhang P.; Xiahou Y.; Song Y.; Bi C.; Zhan J.; Du W.; Huang L.; Möhwald H.; Xia H. ACS Appl. Mater. Interfaces 2018, 10, 23081.

贵金属气凝胶的可控制备及其电催化与表面增强拉曼散射应用

Controlled Synthesis of Noble Metal Aerogels and Their Applications in Electrocatalysis and Surface-Enhanced Raman Scattering

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 12

References 53

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Nannan Wang, Yuzhen Chen. CoNi-MOF-74/NF Derived CoNi@C/NF Hybrid for Efficient Electrosynthesis of Organics [J]. Acta Chimica Sinica, 2024, 82(6): 621-628.
[2]	Shan Li, Junxin Lu, Jie Liu, Lvqi Jiang, Wenbin Yi. Electrochemical Synthesis of α-Fluoroalkylated Ketones using Sodium Fluoroalkylsulfinate [J]. Acta Chimica Sinica, 2024, 82(2): 110-114.
[3]	Zhenhong Yang, Xiaojuan Gan, Shuzhe Wang, Junyuan Duan, Tianyou Zhai, Youwen Liu. Preparation of Metallic Ni₃N Nanoparticles and Its Electrooxidation Performance for Ethylene Glycol^★ [J]. Acta Chimica Sinica, 2023, 81(11): 1471-1477.
[4]	Shaobing Yan, Long Jiao, Chuanxin He, Hailong Jiang. Pyrolysis of ZIF-67/Graphene Composite to Co Nanoparticles Confined in N-Doped Carbon for Efficient Electrocatalytic Oxygen Reduction [J]. Acta Chimica Sinica, 2022, 80(8): 1084-1090.
[5]	Jiawei He, Liu Jiao, Xueyi Cheng, Guanghai Chen, Qiang Wu, Xizhang Wang, Lijun Yang, Zheng Hu. Structural Regulation of Metal Organic Framework-derived Hollow Carbon Nanocages and Their Lithium-Sulfur Battery Performance [J]. Acta Chimica Sinica, 2022, 80(7): 896-902.
[6]	Dan Wang, Bo Feng, Xiaoxin Zhang, Yanan Liu, Yan Pei, Minghua Qiao, Baoning Zong. Nitrogen-doped Carbon Pyrolyzed from ZIF-8 for Electrocatalytic Oxygen Reduction to Hydrogen Peroxide [J]. Acta Chimica Sinica, 2022, 80(6): 772-780.
[7]	Yinlong Jiang, Guochao Li, Qingsong Chen, Zhongning Xu, Shanshan Lin, Guocong Guo. Porous Bismuth Nanoflowers Enriched with Lattice Dislocations for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate^※ [J]. Acta Chimica Sinica, 2022, 80(6): 703-707.
[8]	Pan An, Qinghui Zhang, Zhuang Yang, Jiaxing Wu, Jiaying Zhang, Yajun Wang, Yuming Li, Guiyuan Jiang. Research Progress of Solar Hydrogen Production Technology under Double Carbon Target [J]. Acta Chimica Sinica, 2022, 80(12): 1629-1642.
[9]	Jinge Wang, Wei Zhou, Jiayi Li, Yani Ding, Jihui Gao. Recent Advances and Performance Enhancement Mechanisms of Pulsed Electrocatalysis [J]. Acta Chimica Sinica, 2022, 80(11): 1555-1568.
[10]	Yining Ma, Run Shi, Tierui Zhang. Research Progress on Triphase Interface Electrocatalytic Carbon Dioxide Reduction [J]. Acta Chimica Sinica, 2021, 79(4): 369-377.
[11]	Su Zhan, Fuxiang Zhang. Recent Progress on Electrocatalytic Synthesis of Ammonia Under Amibent Conditions [J]. Acta Chimica Sinica, 2021, 79(2): 146-157.
[12]	Hui He, Lingli Zhou, Zhen Liu. Advances in Protein Biomarker Assay via the Combination of Molecular Imprinting and Surface-enhanced Raman Scattering [J]. Acta Chimica Sinica, 2021, 79(1): 45-57.
[13]	Ren Xuqiang, Li Donglin, Zhao Zhenzhen, Chen Guangqi, Zhao Kun, Kong Xiangze, Li Tongxin. Dual Effect of Aluminum Doping and Lithium Tungstate Coating on the Surface Improves the Cycling Stability of Lithium-rich Manganese-based Cathode Materials [J]. Acta Chimica Sinica, 2020, 78(11): 1268-1274.
[14]	Liu Shengwei, Zhao Jianjun, Xu Yiming. Larger Adsorption Effect of Fluoride than Phosphate on Phenol Degradation over the Irradiated Anatase TiO₂ and Pt/TiO₂ [J]. Acta Chim. Sinica, 2019, 77(4): 351-357.
[15]	Wu Kuangheng, Zhou Yawei, Ma Xianyin, Ding Chen, Cai Wenbin. Controlled Synthesis of Gold-Platinum Catalysts for Ethanol Electro-oxidation Reaction [J]. Acta Chim. Sinica, 2018, 76(4): 292-297.