AgCl/Ag复合粉体材料的制备及机理

摘要/Abstract

摘要： 采用超声辅助脱合金法,以Ca-Mg-Cu-Ag非晶条带为前驱体,Cu-Ag纳米多孔材料为中间产物,不同溶剂组成的盐酸溶液为反应液,制备出不同形貌的AgCl粉体材料,利用SEM、XRD等检测手段对样品的形貌、结构、成分等进行了表征分析,揭示了AgCl/Ag复合粉体材料在不同反应液中的形成过程及机理。研究表明:在超声辅助作用下,当以盐酸乙醇溶液为反应液时,改变浓盐酸溶液与乙醇溶剂的体积比后Cu-Ag纳米多孔材料可以完全溶解于该溶液中并重新析出不同形貌的AgCl粉体材料;而以盐酸水溶液为反应液时,改变盐酸水溶液与蒸馏水溶液的体积比后Cu-Ag纳米多孔材料只能直接转变为近球形的AgCl粉体材料,且不能溶解于盐酸水溶液中再重新析出。在超声与盐酸乙醇溶液的共同作用下,Cu-Ag纳米多孔材料存在一种新颖的AgCl“生成-溶解-再析出”机制,可以精准地控制再析出AgCl晶体的形貌和尺寸。

关键词: AgCl/Ag, 复合粉体材料, 超声辅助, 脱合金法, 形貌

Abstract: AgCl powder materials with different morphologies were prepared by ultrasound-assisted dealloying method using Ca-Mg-Cu-Ag amorphous strips as precursors, Cu-Ag nanoporous material as intermediate product, and hydrochloric acid solutions with different solvent compositions as reaction solution. The morphology, structure, and composition of samples were characterized and analyzed using SEM, XRD and other detection methods, and the formation process and mechanism of AgCl/Ag composite powder material were revealed in different reaction solutions. The results show that under ultrasound-assisted, when using hydrochloric acid ethanol solution as reaction solution, Cu-Ag nanoporous material can be completely dissolved in the solution and then different morphologies of AgCl powder material can be reprecipitated form the same solution after changing the volume ratio of concentrated hydrochloric acid solution to ethanol solvent.When using hydrochloric acid aqueous solution as reaction solution, Cu-Ag nanoporous material can only directly transform into nearly spherical AgCl powder material after changing the volume ratio of hydrochloric acid aqueous solution to distilled water solution, which cannot be dissolved in hydrochloric acid aqueous solution first and then reprecipitated form the same solution. With the coexistance of ultrasound treatment and hydrochloric acid ethanol solution for the Cu-Ag nanoporous material, there exists a novel AgCl ‘formation-dissolution-precipitation’ mechanism, which can be used to accurately control the morphology, structure, and size of the reprecipitated AgCl powder material.

Key words: AgCl/Ag, composite powder material, ultrasound-assisted, dealloying method, morphology

中图分类号:

TB44

杨华键, 赵远云. AgCl/Ag复合粉体材料的制备及机理[J]. 硅酸盐通报, 2024, 43(7): 2697-2705.

YANG Huajian, ZHAO Yuanyun. Preparation and Mechanism of AgCl/Ag Composite Powder Material[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(7): 2697-2705.

参考文献

[1] CAMERON S J, HOSSEINIAN F, WILLMORE W G. A current overview of the biological and cellular effects of nanosilver[J]. International Journal of Molecular Sciences, 2018, 19(7): 2030.
[2] PLOWMAN B J, TSCHULIK K, WALPORT E, et al. The fate of nano-silver in aqueous media[J]. Nanoscale, 2015, 7(29): 12361-12364.
[3] HAN N M, WANG Z Y, SHEN X, et al. Graphene size-dependent multifunctional properties of unidirectional graphene aerogel/epoxy nanocomposites[J]. ACS Applied Materials & Interfaces, 2018, 10(7): 6580-6592.
[4] CHU Z M, JIAO W C, HUANG Y F, et al. FDTS-modified SiO₂/rGO wrinkled films with a micro-nanoscale hierarchical structure and anti-icing/deicing properties under condensation condition[J]. Advanced Materials Interfaces, 2020, 7(1): 1901446.
[5] 刘增泽, 谭芳, 刘燕群. 光催化纳米材料在工业废水处理中的应用[J]. 广州化工, 2021, 49(12): 7-10.
LIU Z Z, TAN F, LIU Y Q. Application of photocatalytic nanomaterials in industrial wastewater treatment[J]. Guangzhou Chemical Industry, 2021, 49(12): 7-10 (in Chinese).
[6] DAMODHARAN J. Nanomaterials in medicine:an overview[J]. Materials Today: Proceedings, 2021, 37: 383-385.
[7] 田野. 纳米Ag/AgCl的生物法制备及特性研究[D]. 哈尔滨: 东北林业大学, 2021.
TIAN Y. Research on biosynthesis of Ag/AgCl nanoparticles and its characteristics[D].Harbin: Northeast Forestry University, 2021 (in Chinese).
[8] HANMANT G S, KORATTI A, POREL M S. Facile tuning of Ag@AgCl cubical hollow nanoframes with efficient sunlight-driven photocatalytic activity[J]. Applied Surface Science, 2019, 465: 413-419.
[9] SU M S, LIU H L, MA J J. Synthesis of cube-like Ag@AgCl photocatalyst with enhanced photocatalytic activity[J]. Journal of Materials Science: Materials in Electronics, 2016, 27(10): 10707-10711.
[10] WANG N N, CHENG K, XU Z F, et al. High-performance natural-sunlight-driven Ag/AgCl photocatalysts with a cube-like morphology and blunt edges via a bola-type surfactant-assisted synthesis[J]. Physical Chemistry Chemical Physics, 2020, 22(7): 3940-3952.
[11] LI B H, WU S F, GAO X S. Theoretical calculation of a TiO₂-based photocatalyst in the field of water splitting: a review[J]. Nanotechnology Reviews, 2020, 9(1): 1080-1103.
[12] LIU C H, HUANG C Y, LEE P C, et al. AgCl-based selective laser melting photocatalytic module for degradation of azo dye and E. coli[J]. The International Journal of Advanced Manufacturing Technology, 2021, 115(4): 1127-1138.
[13] QIN Z J, ZHENG Y K, WANG Y H, et al. Versatile roles of silver in Ag-based nanoalloys for antibacterial applications[J]. Coordination Chemistry Reviews, 2021, 449: 214218.
[14] BOLAÑOS-BENÍTEZ V, MCDERMOTT F, GILL L, et al. Engineered silver nanoparticle (Ag-NP) behaviour in domestic on-site wastewater treatment plants and in sewage sludge amended-soils[J]. Science of the Total Environment, 2020, 722: 137794.
[15] LIM B, XIA Y N. Metal nanocrystals with highly branched morphologies[J]. Angewandte Chemie International Edition, 2011, 50(1): 76-85.
[16] 阎修业. 水热法合成Ag@AgCl还原氧化石墨烯复合材料及其光催化性能研究[D]. 武汉: 武汉科技大学, 2013.
YAN X Y. Hydrothermal synthesis and photocatalytic properties of composites of Ag@AgCl and reduced graphene oxide[D].Wuhan: Wuhan University of Science and Technology, 2013 (in Chinese).
[17] 王婉. 模板法制备Ag/AgCl基可见光催化剂及其性能研究[D]. 开封: 河南大学, 2018.
WANG W. Photocatalytic properties of Ag/AgCl-based visible-light-driven photocatalysts synthesizd by template method[D].Kaifeng: Henan University, 2018 (in Chinese).
[18] AZARAKHSH S, BAHIRAEI H, HAIDARI G. Electrospun synthesis of silver/poly (vinyl alcohol) nano-fibers: investigation of microstructure and antibacterial activity[J]. Materials Letters, 2022, 309: 131370.
[19] SHEN Y F, CHEN P L, XIAO D, et al. Spherical and sheetlike Ag/AgCl nanostructures: interesting photocatalysts with unusual facet-dependent yet substrate-sensitive reactivity[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2015, 31(1): 602-610.
[20] WANG Y P, CHEN P L, SHEN Y F, et al. Visible-light-driven Ag/AgCl plasmonic photocatalysts via a surfactant-assisted protocol: enhanced catalytic performance by morphology evolution from near-spherical to 1D structures[J]. Physical Chemistry Chemical Physics: PCCP, 2015, 17(38): 25182-25190.
[21] DAUPOR H, WONGNAWA S. Flower-like Ag/AgCl microcrystals: synthesis and photocatalytic activity[J]. Materials Chemistry and Physics, 2015, 159: 71-82.
[22] JIA C C, YANG P, HUANG B B. Uniform Ag/AgCl necklace-like nano-heterostructures: fabrication and highly efficient plasmonic photocatalysis[J]. ChemCatChem, 2014, 6(2): 611-617.
[23] AN C H, PENG S, SUN Y G. Facile synthesis of sunlight-driven AgCl: Ag plasmonic nanophotocatalyst[J]. Advanced Materials, 2010, 22(23): 2570-2574.
[24] HAN L, WANG P, ZHU C Z, et al. Facile solvothermal synthesis of cube-like Ag@AgCl: a highly efficient visible light photocatalyst[J]. Nanoscale, 2011, 3(7): 2931-2935.
[25] TANG Y X, JIANG Z L, XING G C, et al. Efficient Ag@AgCl cubic cage photocatalysts profit from ultrafast plasmon-induced electron transfer processes[J]. Advanced Functional Materials, 2013, 23(23): 2932-2940.
[26] ZHAO Y Y, QIAN F, ZHAO C L, et al. Facile fabrication of ultrathin freestanding nanoporous Cu and Cu-Ag films with high SERS sensitivity by dealloying Mg-Cu(Ag)-Gd metallic glasses[J]. Journal of Materials Science & Technology, 2021, 70: 205-213.
[27] WANG J Y, QIN Y Z, SHI Q C, et al. Cl^--induced selective fabrication of 3D AgCl microcrystals by a one-pot synthesis method[J]. CrystEngComm, 2021, 23(29): 5116-5123.