等离激元金属-半导体复合电极的界面声子热输运特性

郑子超; 李志康; 桑丽霞

doi:10.7498/aps.74.20250683

摘要

为了优选等离激元太阳能分解水体系中金属和半导体的复合光电极, 本文采用非平衡分子动力学方法计算了等离激元金属Cu, Ag和Au与半导体TiO₂, ZnO和MoS₂的复合电极在不同温度下的界面热导, 并通过计算声子态密度和声子参与率研究了不同频率的声子与界面热导的关系. 结果表明, 随温度的增加, 不同复合电极的界面热导增加. 在相同的半导体TiO₂上, Cu-TiO₂和Ag-TiO₂界面热导均高于Au-TiO₂, Cu-TiO₂复合电极的界面热导在800 K时可以达到973.56 MW·m^–2·K^–1. 对于等离激元金属Au, 相对MoS₂和TiO₂, 其与ZnO复合的界面导热更高; 而对于等离激元金属Cu, Cu-TiO₂的界面热导高于预测的Cu-ZnO, 这取决于更多处于核心热输运频段的低频声子参与界面热输运.

关键词:

Abstract

Plasmonic solar water splitting is produced on the composite electrode with plasmonic metal nanoparticles loaded on semiconductor, where the localized heating generated by relaxation of the metal’s localized surface plasmon resonance (LSPR) under light excitation enhances hydrogen production efficiency. To optimize composite photoanodes for photoelectrochemical water splitting system, the non-equilibrium molecular dynamics simulations are conducted to obtain the interfacial thermal conductivity between plasmonic metals (Cu, Ag, Au) and semiconductors (TiO₂, ZnO, MoS₂) at varying temperatures. The relationship between interfacial thermal conductivity and phonons at different frequencies is investigated via vibrational density of states which is calculated from the velocity autocorrelation functions and subsequent phonon participation ratio. The results indicate that as he temperature increases, the interfacial thermal conductivity of all composite electrode configurations is enhanced. When Cu and Ag are combined with TiO₂ into Cu-TiO₂ and Ag-TiO₂, respectively, the thermal transport performances of Cu-TiO₂ and Ag-TiO₂ are superior to Au-TiO₂, and the interfacial thermal conductivity of Cu-TiO₂ reaches 973.56 MW·m^–2·K^–1 at 800 K. With Au as the fixed plasmonic component, Au-ZnO shows that its interfacial thermal conductivity reaches 324.44 MW·m^–2·K^–1 at 800 K, which is higher than those of Au-MoS₂ and Au-TiO₂. Based on the obtained interfacial thermal conductivity of different composite photoanodes, it is predicted that Cu-ZnO is the optimal composite, but its interfacial thermal conductivity is 547.69 MW·m^–2·K^–1 at 800 K, second only to Cu-TiO₂. The analysis of vibrational density of states and phonon participation ratio shows that the low-frequency region (0—10 THz) is the main region for thermal transport, and both interfaces exhibit a high phonon participation ratio range of 0.7—0.8. However, the Cu-TiO₂ possesses much higher vibrational density of states than Cu-ZnO within this critical band. Although Cu-ZnO exhibits a higher phonon participation ratio range in the high-frequency range, its lower overall interfacial thermal conductivity is attributed to the minimal contribution of high-frequency phonons to interfacial thermal conductance. The findings provide optimization strategies based on interfacial thermal transport mechanisms for constructing efficient photoanodes for solar water splitting.

Keywords:

作者及机构信息

北京工业大学, 传热与能源利用北京市重点实验室, 北京　100124

通信作者: 桑丽霞, sanglixia@bjut.edu.cn

基金项目: 国家自然科学基金(批准号: 52176174)资助的课题.

Authors and contacts

Beijing Key Laboratory of Heat Transfer and Energy Conversion, Beijing University of Technology, Beijing 100124, China

Corresponding author: SANG Lixia, sanglixia@bjut.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 52176174).

文章全文

参考文献

[1]	Cavigli L, Milanesi A, Khlebtsov B N, Centi S, Ratto F, Khlebtsov N G, Pini R 2020 J. Colloid Interface Sci. 578 358 Google Scholar
[2]	Czelej K, Colmenares J C, Jabłczyńska K, Ćwieka K, Werner Ł, Gradoń L 2021 Catal. Today 380 156 Google Scholar
[3]	Ghosh U, Pal A, Pal T 2022 Adv. Mater. Interfaces 9 2200465 Google Scholar
[4]	Lou Y B, Zhang Y K, Cheng L, Chen J X, Zhao Y X 2018 ChemSusChem 11 1505 Google Scholar
[5]	Liu L D, Zhang H F, Xing S, Zhang Y, Li S G, Wei C, Peng F, Liu X Y 2023 Adv. Sci. 10 2207342 Google Scholar
[6]	Sang L X, Wang C, Zhao Y, Ren Z Y 2023 J. Phys. Chem. C 127 14666 Google Scholar
[7]	Zhao W R, Ai Z Y, Dai J S, Zhang M 2014 PLoS ONE 9 e103671 Google Scholar
[8]	Zhai H S, Liu X L, Wang Z Y, Liu Y Y, Zheng Z K, Qin X Y, Zhang X Y, Wang P, Huang B B 2020 Chin. J. Catal. 41 1613 Google Scholar
[9]	Li Y Y, Wu S, Zheng J W, Peng Y K, Prabhakaran D, Taylor R A, Tsang S C E 2020 Mater. Today 41 34 Google Scholar
[10]	桑丽霞, 马梦楠 2023 高等学校化学学报 44 20220768 Google Scholar Sang L X, Ma M N 2023 Chem. J. Chin. Uiv. 44 20220768 Google Scholar
[11]	桑丽霞, 李志康 2024 73 103105 Google Scholar Sang L X, Li Z K 2024 Acta Phys. Sin. 73 103105 Google Scholar
[12]	Swartz E T, Pohl R O 1989 Rev. Mod. Phys. 61 605 Google Scholar
[13]	Kunthakudee N, Puangpetch T, Ramakul P, Serivalsatit K, Hunsom M 2022 Int. J. Hydrogen Energy 47 23570 Google Scholar
[14]	Meng H, Maruyama S G, Xiang R, Yang N 2021 Int. J. Heat Mass Transfer 180 121773 Google Scholar
[15]	Lu Z X, Wang Y, Ruan X L 2016 Phys. Rev. B 93 064302 Google Scholar
[16]	Majumdar A, Reddy P 2004 Appl. Phys. Lett. 84 4768 Google Scholar
[17]	宗志成, 潘东楷, 邓世琛, 万骁, 杨哩娜, 马登科, 杨诺 2023 72 034401 Google Scholar Zong Z C, Pan D K, Deng S C, Wan X, Yang L N, Ma D K, Yang N 2023 Acta Phys. Sin. 72 034401 Google Scholar
[18]	Giri A, Gaskins J T, Donovan B F, Szwejkowski C, Warzoha R J, Rodriguez M A, Ihlefeld J, Hopkins P E 2015 J. Appl. Phys. 117 105105 Google Scholar
[19]	Giri A, Hopkins P E 2020 Adv. Funct. Mater. 30 1903857 Google Scholar
[20]	Wu X, Han Q 2021 ACS Appl. Mater. Interfaces 13 32564 Google Scholar
[21]	Loh G C, Teo E H T, Tay B K 2012 Diamond Relat. Mater. 23 88 Google Scholar
[22]	Robert S, Leonid Z, Pamela N 2007 Int. J. Heat Mass Transfer 50 3977 Google Scholar
[23]	Samy M, Konstantinos T 2012 Phys. Rev. B 86 094303 Google Scholar
[24]	Tang Z Y, Wang X X, He C Y, Li J, Chen M X, Tang C, Ouyang T 2024 Phys. Rev. B 110 134320 Google Scholar
[25]	Li Z D, Han L W, Ouyang T, Cao J X, Yao Y S, Wei X L 2025 Phys. Rev. Mater. 9 033804 Google Scholar
[26]	Liu Y, Wu W H, Yang S X, Yang P 2022 Surf. Interfaces 28 101640 Google Scholar
[27]	Wang W D, Pi Z L, Lei F, Lu Y 2016 AIP Adv. 6 035111 Google Scholar
[28]	Plimpton S 1995 J. Comput. Phys. 117 1 Google Scholar
[29]	Zong Z C, Deng S C, Qin Y J, Wan X, Zhan J H, Ma D K, Yang N 2023 Nanoscale 15 16472 Google Scholar
[30]	Lin G, Jiang L, Ji P F 2023 Phys. Chem. Chem. Phys. 25 19853 Google Scholar
[31]	Liu X J, Zhang G, Zhang Y W 2016 Nano Res. 9 2372 Google Scholar
[32]	Namsani S, Singh J K 2018 J. Phys. Chem. C 122 2113 Google Scholar
[33]	Pei Q X, Guo J Y, Suwardi A, Zhang G 2023 J. Phys. Chem. C 127 19796 Google Scholar
[34]	Sheng Y F, Hu Y, Fan Z Y, Bao H 2022 Phys. Rev. B 105 075301 Google Scholar
[35]	刘东静, 王韶铭, 杨平 2021 70 187302 Google Scholar Liu D J, Wang S M, Yang P 2021 Acta Phys. Sin. 70 187302 Google Scholar
[36]	Lu C C, Li Z H, Li S C, Li Z, Zhang Y Y, Zhao J H, Wei N 2023 Carbon 213 118250 Google Scholar
[37]	Zhou H B, Zhang G 2018 Chin. Phys. B 27 034401 Google Scholar

施引文献

图 1 不同复合电极的原子结构　(a) Cu-TiO₂; (b) Ag-TiO₂; (c) Au-ZnO; (d) Au-MoS₂

Fig. 1. Atomic structures of different composite electrodes: (a) Cu-TiO₂; (b) Ag-TiO₂; (c) Au-ZnO; (d) Au-MoS₂.

下载: 全尺寸图片幻灯片

图 2 不同温度下Au-TiO₂^[11], Ag-TiO₂和Cu-TiO₂复合电极的界面热导

Fig. 2. Interfacial thermal conductivity of Au-TiO₂^[11], Ag-TiO₂ and Cu-TiO₂ composite electrodes with different temperatures.

下载: 全尺寸图片幻灯片

图 3 Cu-TiO₂复合电极各组分在不同温度下的声子态密度　(a) TiO₂; (b) Cu

Fig. 3. VDOS of each component in Cu-TiO₂ composite electrode at different temperatures: (a) TiO₂; (b) Cu.

下载: 全尺寸图片幻灯片

图 4 Ag-TiO₂复合电极各组分在不同温度下的声子态密度　(a) TiO₂; (b) Ag

Fig. 4. VDOS of each component in Ag-TiO₂ composite electrode at different temperatures: (a) TiO₂; (b) Ag.

下载: 全尺寸图片幻灯片

图 5 不同温度下各组分的声子态密度　(a) 300 K; (b) 400 K; (c) 500 K; (d) 600 K; (e) 700 K; (f) 800 K

Fig. 5. Phonon density of states for each component at different temperatures: (a) 300 K; (b) 400 K; (c) 500 K; (d) 600 K; (e) 700 K; (f) 800 K.

下载: 全尺寸图片幻灯片

图 6 不同温度下Au-TiO₂^[11], Au-MoS₂和Au-ZnO复合电极的界面热导

Fig. 6. Interfacial thermal conductivity of Au-TiO₂^[11], Au-MoS₂ and Au-ZnO composite electrodes at different temperatures.

下载: 全尺寸图片幻灯片

图 7 不同温度时Au-MoS₂复合电极的声子态密度　(a) 400 K; (b) 500 K; (c) 600 K; (d) 700 K

Fig. 7. Phonon density of states for Au-MoS₂ composite electrodes at different temperatures: (a) 400 K; (b) 500 K; (c) 600 K; (d) 700 K.

下载: 全尺寸图片幻灯片

图 8 不同温度时Au-ZnO复合电极的声子态密度　(a) 400 K; (b) 500 K; (c) 600 K; (d) 700 K

Fig. 8. Phonon density of states for Au-ZnO composite electrodes at different temperatures: (a) 400 K; (b) 500 K; (c) 600 K; (d) 700 K.

下载: 全尺寸图片幻灯片

图 9 不同温度下Cu-ZnO复合电极的界面热导

Fig. 9. Interfacial thermal conductivity of Cu-ZnO composite electrodes at different temperatures.

下载: 全尺寸图片幻灯片

图 10 不同温度下各组分的声子态密度　(a), (b) 300 K; (c), (d) 400 K; (e), (f) 500 K; (g), (h) 600 K

Fig. 10. Phonon density of states for each component at different temperatures: (a), (b) 300 K; (c), (d) 400 K; (e), (f) 500 K; (g), (h) 600 K.

下载: 全尺寸图片幻灯片

图 11 不同温度下, Cu-ZnO和Cu-TiO₂界面的声子参与率　(a) 300 K; (b) 600 K

Fig. 11. Phonon participation at Cu-ZnO and Cu-TiO₂ interfaces at different temperatures: (a) 300 K; (b) 600 K.

下载: 全尺寸图片幻灯片

表 1 ZnO的势函数参数^[27]

Table 1. Potential function parameters of ZnO^[27].

A_ij/(kcal·mol^–1) B_ij/(kcal·mol^–1·Å⁶) ρ_ij/Å

Zn—Zn 1819.71 0.00 0.5177
Zn—O 5940396 0.00 0.1396
O—O 271720 696.95 0.235

下载: 导出CSV

map

[1]	Cavigli L, Milanesi A, Khlebtsov B N, Centi S, Ratto F, Khlebtsov N G, Pini R 2020 J. Colloid Interface Sci. 578 358 Google Scholar
[2]	Czelej K, Colmenares J C, Jabłczyńska K, Ćwieka K, Werner Ł, Gradoń L 2021 Catal. Today 380 156 Google Scholar
[3]	Ghosh U, Pal A, Pal T 2022 Adv. Mater. Interfaces 9 2200465 Google Scholar
[4]	Lou Y B, Zhang Y K, Cheng L, Chen J X, Zhao Y X 2018 ChemSusChem 11 1505 Google Scholar
[5]	Liu L D, Zhang H F, Xing S, Zhang Y, Li S G, Wei C, Peng F, Liu X Y 2023 Adv. Sci. 10 2207342 Google Scholar
[6]	Sang L X, Wang C, Zhao Y, Ren Z Y 2023 J. Phys. Chem. C 127 14666 Google Scholar
[7]	Zhao W R, Ai Z Y, Dai J S, Zhang M 2014 PLoS ONE 9 e103671 Google Scholar
[8]	Zhai H S, Liu X L, Wang Z Y, Liu Y Y, Zheng Z K, Qin X Y, Zhang X Y, Wang P, Huang B B 2020 Chin. J. Catal. 41 1613 Google Scholar
[9]	Li Y Y, Wu S, Zheng J W, Peng Y K, Prabhakaran D, Taylor R A, Tsang S C E 2020 Mater. Today 41 34 Google Scholar
[10]	桑丽霞, 马梦楠 2023 高等学校化学学报 44 20220768 Google Scholar Sang L X, Ma M N 2023 Chem. J. Chin. Uiv. 44 20220768 Google Scholar
[11]	桑丽霞, 李志康 2024 73 103105 Google Scholar Sang L X, Li Z K 2024 Acta Phys. Sin. 73 103105 Google Scholar
[12]	Swartz E T, Pohl R O 1989 Rev. Mod. Phys. 61 605 Google Scholar
[13]	Kunthakudee N, Puangpetch T, Ramakul P, Serivalsatit K, Hunsom M 2022 Int. J. Hydrogen Energy 47 23570 Google Scholar
[14]	Meng H, Maruyama S G, Xiang R, Yang N 2021 Int. J. Heat Mass Transfer 180 121773 Google Scholar
[15]	Lu Z X, Wang Y, Ruan X L 2016 Phys. Rev. B 93 064302 Google Scholar
[16]	Majumdar A, Reddy P 2004 Appl. Phys. Lett. 84 4768 Google Scholar
[17]	宗志成, 潘东楷, 邓世琛, 万骁, 杨哩娜, 马登科, 杨诺 2023 72 034401 Google Scholar Zong Z C, Pan D K, Deng S C, Wan X, Yang L N, Ma D K, Yang N 2023 Acta Phys. Sin. 72 034401 Google Scholar
[18]	Giri A, Gaskins J T, Donovan B F, Szwejkowski C, Warzoha R J, Rodriguez M A, Ihlefeld J, Hopkins P E 2015 J. Appl. Phys. 117 105105 Google Scholar
[19]	Giri A, Hopkins P E 2020 Adv. Funct. Mater. 30 1903857 Google Scholar
[20]	Wu X, Han Q 2021 ACS Appl. Mater. Interfaces 13 32564 Google Scholar
[21]	Loh G C, Teo E H T, Tay B K 2012 Diamond Relat. Mater. 23 88 Google Scholar
[22]	Robert S, Leonid Z, Pamela N 2007 Int. J. Heat Mass Transfer 50 3977 Google Scholar
[23]	Samy M, Konstantinos T 2012 Phys. Rev. B 86 094303 Google Scholar
[24]	Tang Z Y, Wang X X, He C Y, Li J, Chen M X, Tang C, Ouyang T 2024 Phys. Rev. B 110 134320 Google Scholar
[25]	Li Z D, Han L W, Ouyang T, Cao J X, Yao Y S, Wei X L 2025 Phys. Rev. Mater. 9 033804 Google Scholar
[26]	Liu Y, Wu W H, Yang S X, Yang P 2022 Surf. Interfaces 28 101640 Google Scholar
[27]	Wang W D, Pi Z L, Lei F, Lu Y 2016 AIP Adv. 6 035111 Google Scholar
[28]	Plimpton S 1995 J. Comput. Phys. 117 1 Google Scholar
[29]	Zong Z C, Deng S C, Qin Y J, Wan X, Zhan J H, Ma D K, Yang N 2023 Nanoscale 15 16472 Google Scholar
[30]	Lin G, Jiang L, Ji P F 2023 Phys. Chem. Chem. Phys. 25 19853 Google Scholar
[31]	Liu X J, Zhang G, Zhang Y W 2016 Nano Res. 9 2372 Google Scholar
[32]	Namsani S, Singh J K 2018 J. Phys. Chem. C 122 2113 Google Scholar
[33]	Pei Q X, Guo J Y, Suwardi A, Zhang G 2023 J. Phys. Chem. C 127 19796 Google Scholar
[34]	Sheng Y F, Hu Y, Fan Z Y, Bao H 2022 Phys. Rev. B 105 075301 Google Scholar
[35]	刘东静, 王韶铭, 杨平 2021 70 187302 Google Scholar Liu D J, Wang S M, Yang P 2021 Acta Phys. Sin. 70 187302 Google Scholar
[36]	Lu C C, Li Z H, Li S C, Li Z, Zhang Y Y, Zhao J H, Wei N 2023 Carbon 213 118250 Google Scholar
[37]	Zhou H B, Zhang G 2018 Chin. Phys. B 27 034401 Google Scholar

[1]	李丽丽, 韩爽, 王玉龙, 刘统江, 李育哲, 高俊国. 氢键对聚丙烯复合材料分子结构与电荷输运特性的影响. , 2025, 74(12): 127702. doi: 10.7498/aps.74.20250277
[2]	桑丽霞, 李志康. Au-TiO₂光电极界面声子热输运特性的分子动力学模拟. , 2024, 73(10): 103105. doi: 10.7498/aps.73.20240026
[3]	杨权, 马立, 耿松超, 林旖旎, 陈涛, 孙立宁. 多壁碳纳米管与金属表面间接触行为的分子动力学模拟. , 2021, 70(10): 106101. doi: 10.7498/aps.70.20202194
[4]	赵中华, 渠广昊, 姚佳池, 闵道敏, 翟鹏飞, 刘杰, 李盛涛. 热峰作用下单斜ZrO₂相变过程的分子动力学模拟. , 2021, 70(13): 136101. doi: 10.7498/aps.70.20201861
[5]	梅涛, 陈占秀, 杨历, 朱洪漫, 苗瑞灿. 非对称纳米通道内界面热阻的分子动力学研究. , 2020, 69(22): 224701. doi: 10.7498/aps.69.20200491
[6]	张忠强, 李冲, 刘汉伦, 葛道晗, 程广贵, 丁建宁. 石墨烯碳纳米管复合结构渗透特性的分子动力学研究. , 2018, 67(5): 056102. doi: 10.7498/aps.67.20172424
[7]	李丽丽, Xia Zhen-Hai, 杨延清, 韩明. SiC纳米纤维/C/SiC复合材料拉伸行为的分子动力学研究. , 2015, 64(11): 117101. doi: 10.7498/aps.64.117101
[8]	张金平, 张洋洋, 李慧, 高景霞, 程新路. 纳米铝热剂Al/SiO2层状结构铝热反应的分子动力学模拟. , 2014, 63(8): 086401. doi: 10.7498/aps.63.086401
[9]	张程宾, 程启坤, 陈永平. 分形结构纳米复合材料热导率的分子动力学模拟研究. , 2014, 63(23): 236601. doi: 10.7498/aps.63.236601
[10]	唐翠明, 赵锋, 陈晓旭, 陈华君, 程新路. Al与α-Fe2O3纳米界面铝热反应的从头计算分子动力学研究. , 2013, 62(24): 247101. doi: 10.7498/aps.62.247101
[11]	陈敏. 分子动力学方法研究金属Ti中He小团簇的迁移. , 2011, 60(12): 126602. doi: 10.7498/aps.60.126602
[12]	陈俊, 史琳, 王楠, 毕胜山. 基于分子动力学模拟流体输运性质的稳定性分析. , 2011, 60(12): 126601. doi: 10.7498/aps.60.126601
[13]	马文, 祝文军, 张亚林, 陈开果, 邓小良, 经福谦. 纳米多晶金属样本构建的分子动力学模拟研究. , 2010, 59(7): 4781-4787. doi: 10.7498/aps.59.4781
[14]	陈开果, 祝文军, 马文, 邓小良, 贺红亮, 经福谦. 冲击波在纳米金属铜中传播的分子动力学模拟. , 2010, 59(2): 1225-1232. doi: 10.7498/aps.59.1225
[15]	何安民, 秦承森, 邵建立, 王裴. 金属Al表面熔化各向异性的分子动力学模拟. , 2009, 58(4): 2667-2674. doi: 10.7498/aps.58.2667
[16]	周宗荣, 王宇, 夏源明. γ-TiAl金属间化合物面缺陷能的分子动力学研究. , 2007, 56(3): 1526-1531. doi: 10.7498/aps.56.1526
[17]	周国荣, 高秋明. 金属Ni纳米线凝固行为的分子动力学模拟. , 2007, 56(3): 1499-1505. doi: 10.7498/aps.56.1499
[18]	王海龙, 王秀喜, 梁海弋. 应变效应对金属Cu表面熔化影响的分子动力学模拟. , 2005, 54(10): 4836-4841. doi: 10.7498/aps.54.4836
[19]	陈军, 经福谦, 张景琳, 陈栋泉. 冲击作用下金属表面微喷射的分子动力学模拟. , 2002, 51(10): 2386-2392. doi: 10.7498/aps.51.2386
[20]	吴恒安, 倪向贵, 王宇, 王秀喜. 金属纳米棒弯曲力学行为的分子动力学模拟. , 2002, 51(7): 1412-1415. doi: 10.7498/aps.51.1412

计量

文章访问数: 421
PDF下载量: 7
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板

等离激元金属-半导体复合电极的界面声子热输运特性