Interfacial phonon thermal transport properties of plasmonic-metal-semiconductor composite electrodes

ZHENG Zichao; LI Zhikang; SANG Lixia

doi:10.7498/aps.74.20250683

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:

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).

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References

[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

Cited By

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

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

DownLoad: Full-Size Img PowerPoint

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

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

DownLoad: Full-Size Img PowerPoint

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

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

DownLoad: Full-Size Img PowerPoint

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

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

DownLoad: Full-Size Img PowerPoint

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

Figure 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.

DownLoad: Full-Size Img PowerPoint

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

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

DownLoad: Full-Size Img PowerPoint

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

Figure 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.

DownLoad: Full-Size Img PowerPoint

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

Figure 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.

DownLoad: Full-Size Img PowerPoint

图 9 不同温度下Cu-ZnO复合电极的界面热导

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

DownLoad: Full-Size Img PowerPoint

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

Figure 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.

DownLoad: Full-Size Img PowerPoint

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

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

DownLoad: Full-Size Img PowerPoint

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

DownLoad: 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

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Vol. 74, Issue 19 - 2025-10-05

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