In-situ formation of electron-deficient Pd sites on AuPd alloy nanoparticles under irradiation enabled efficient photocatalytic Heck reaction

doi:10.1016/S1872-2067(22)64192-5

Abstract

Abstract:

Plasmonic metal nanoparticles have emerged as important candidates for photocatalysis. Numerous studies have shown that coupling of a plasmonic component (such as Au) as the light energy harvester with a catalytically active metal component (such as Pd) to form hybrid or alloy structures could achieve enhanced catalytic performance. However, the microscopic mechanism relative to the multicomponent plasmonic photocatalysis is still elusive. Here, we find that the electron-deficient Pd sites (Pd^δ⁺) on AuPd alloy nanoparticle were formed under visible light irradiation, which play a decisive role in the AuPd alloy nanoparticle photocatalysis. The in-situ formed Pd^δ⁺ under irradiation offers ideal platform for the catalytic reaction which is comparable to that under thermal heating conditions (>100 °C). The AuPd alloy nanoparticles show excellent conversion and selectivity for visible-light-driven Heck cross-coupling reaction under ambient conditions. The combination of experimental and density functional theory results suggest that the photocatalytic Heck reaction proceeds via a new radical-based single-electron transfer pathway on the AuPd alloy, and the in-situ formed Pd^δ⁺ sites ideally provided efficient catalytic sites for the activation of reactant with much lower activation energy barrier under irradiation. The present work sheds light on the new mechanistic understandings of bimetallic plasmonic photocatalysis.

Key words: Plasmonic photocatalysis, AuPd alloy, Electron-deficient Pd, Surface charge state, Photocatalytic Heck reaction

Haifeng Wang, Fan Wang, Xiaopeng Li, Qi Xiao, Wei Luo, Jingsan Xu. In-situ formation of electron-deficient Pd sites on AuPd alloy nanoparticles under irradiation enabled efficient photocatalytic Heck reaction[J]. Chinese Journal of Catalysis, 2023, 46: 72-83.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64192-5

https://www.cjcatal.com/EN/Y2023/V46/I3/72

Figures/Tables 9

Fig. 1. HRTEM (a,b), HAADF (c) images and corresponding EDS atomic elemental mappings (d-f) of AuPd/ZrO2.

Fig. 2. XRD patterns (a), UV-vis spectra (b), high-resolution XPS spectra of Au 4f (c) and Pd 3d (d) of M/ZrO2.

Fig. 3. In-situ high-resolution XPS spectra of AuPd/ZrO2. Au 4f (a) and Pd 3d (b) at different irradiation time intervals; Au 4f (c) and Pd 3d (d) at different heating temperatures.

Fig. 4. Photocatalytic Heck reactions that utilize various Au/Pd ratio catalysts with 3-iodotoluene and styrene as the reactants under visible light irradiation at 40 °C, and a control dark experiment with AuPd/ZrO2 catalyst at 100 °C.

Table 1 Photocatalytic activities of Heck cross-coupling reactions using different aryl iodides to react with styrene.

Entry	Conversion (%)	Selectivity (%)
1	93	>99
2	75	>99
3	41	>99
4	88	>99
5	18	>99
6	25	>99

Fig. 5. (a) The dependence of the catalytic activity of AuPd/ZrO2 catalyst for Heck reaction on the light intensity. (b) The action spectra for Heck reaction. The light absorption spectrum (left axis) is the normalized DR-UV-vis absorption of the AuPd/ZrO2 catalyst (blue curve). (c) The catalytic activities of the Heck reaction using AuPd/ZrO2 catalyst at different temperatures under visible-light irradiation (red dot) and in the dark (blue dot). (d) Apparent activation energy calculated for the photocatalytic reaction and the reaction in the dark. All the reactions use 3-iodotoluene as substrate to react with styrene under typical reaction conditions (except for the light intensity, wavelength and temperature as applied).

Fig. 6. IES spectra of the iodobenzene adsorbed on AuPd/ZrO2 catalyst (a) and the support ZrO2 (b). IES spectra of styrene adsorbed AuPd/ZrO2 catalyst (c) and the support ZrO2 (d). The temperature is increased from 100 to 600 °C, and the increased temperature interval is 50 °C following the arrow from down to top.

Fig. 7. The photocatalytic Heck reaction in the presence of specific scavengers for mechanism study.

Fig. 8. (a) Potential energy surface of iodobenzene dissociation over Pd (111) and an electron-deficient Pd (111) surface. (b) Proposed photocatalytic Heck reaction mechanism.

References

[1]	A. Gellé, T. Jin, L. de la Garza, G. D. Price, L. V. Besteiro, A. Moores, Chem. Rev., 2020, 120, 986-1041.
[2]	D. Friedmann, A. Hakki, H. Kim, W. Choi, D. Bahnemann, Green Chem., 2016, 18, 5391-5411.
[3]	M. H. Shaw, J. Twilton, D. W. C. MacMillan, J. Org. Chem., 2016, 81, 6898-6926.
[4]	T. Noël, E. Zysman-Colman, Chem. Catal., 2022, 2, 468-476.
[5]	H. Yang, K. Dai, J. Zhang, G. Dawson, Chin. J. Catal., 2022, 43, 2111-2140.
[6]	J. Tang, L. Wang, R. Godin, R. Marschall, Chin. J. Catal., 2022, 43, 2271-2272.
[7]	W.-M. He, Chin. J. Catal., 2022, 43, 547.
[8]	J. Ma, X. Li, Y. Li, G. Jiao, H. Su, D. Xiao, S. Zhai, R. Sun, Adv. Powder Mater., 2022, 1, 100058.
[9]	S. Linic, U. Aslam, C. Boerigter, M. Morabito, Nat. Mater., 2015, 14, 567-576.
[10]	H. Wang, X. Li, Y. Jiang, M. Li, Q. Xiao, T. Zhao, S. Yang, C. Qi, P. Qiu, J. Yang, Z. Jiang, W. Luo, Angew. Chem. Int. Ed., 2022, 61, e202200465.
[11]	Q. Xiao, E. Jaatinen, H. Zhu, Chem. Asian J., 2014, 9, 3046-3064.
[12]	S. Sarina, H. Zhu, E. Jaatinen, Q. Xiao, H. Liu, J. Jia, C. Chen, J. Zhao, J. Am. Chem. Soc., 2013, 135,5793-5801.
[13]	F. Wang, C. Li, H. Chen, R. Jiang, L.-D. Sun, Q. Li, J. Wang, J. C. Yu, C.-H. Yan, J. Am. Chem. Soc., 2013, 135, 5588-5601.
[14]	Z. Zheng, T. Tachikawa, T. Majima, J. Am. Chem. Soc., 2015, 137, 948-957.
[15]	D. F. Swearer, H. Zhao, L. Zhou, C. Zhang, H. Robatjazi, J. M. P. Martirez, C. M. Krauter, S. Yazdi, M. J. McClain, E. Ringe, E. A. Carter, P. Nordlander, N. J. Halas, Proc. Natl. Acad. Sci. U. S. A., 2016, 113, 8916-8920.
[16]	J. Guo, Y. Zhang, L. Shi, Y. Zhu, M. F. Mideksa, K. Hou, W. Zhao, D. Wang, M. Zhao, X. Zhang, J. Lv, J. Zhang, X. Wang, Z. Tang, J. Am. Chem. Soc., 2017, 139, 17964-17972.
[17]	Q. Xiao, Z. Liu, A. Bo, S. Zavahir, S. Sarina, S. Bottle, J. D. Riches, H. Zhu, J. Am. Chem. Soc., 2015, 137, 1956-1966.
[18]	T. Chen, F. Tong, J. Enderlein, Z. Zheng, Nano Lett., 2020, 20, 3326-3330.
[19]	L. Zhou, J. M. P. Martirez, J. Finzel, C. Zhang, D. F. Swearer, S. Tian, H. Robatjazi, M. Lou, L. Dong, L. Henderson, P. Christopher, E. A. Carter, P. Nordlander, N. J. Halas, Nat. Energy, 2020, 5, 61-70.
[20]	H. Robatjazi, J. L. Bao, M. Zhang, L. Zhou, P. Christopher, E. A. Carter, P. Nordlander, N. J. Halas, Nat. Catal., 2020, 3, 564-573.
[21]	M.-Y. Qi, H.-K. Wu, M. Anpo, Z.-R. Tang, Y.-J. Xu, Nano Res., 2022, 15, 9967-9975.
[22]	Q. Xiao, S. Sarina, A. Bo, J. Jia, H. Liu, D. P. Arnold, Y. Huang, H. Wu, H. Zhu, ACS Catal., 2014, 4, 1725-1734.
[23]	Q. Xiao, S. Sarina, E. Jaatinen, J. Jia, D. P. Arnold, H. Liu, H. Zhu, Green Chem., 2014, 16, 4272-4285.
[24]	S. K. Movahed, S. Miraghaee, M. Dabiri, J. Alloys Compd., 2020, 819, 152994.
[25]	H. Jiang, J. Xu, S. Zhang, H. Cheng, C. Zang, F. Bian, Catal. Sci. Technol., 2021, 11, 219-229.
[26]	X. Huang, O. Akdim, M. Douthwaite, K. Wang, L. Zhao, R. J. Lewis, S. Pattisson, I. T. Daniel, P. J. Miedziak, G. Shaw, D. J. Morgan, S. M. Althahban, T. E. Davies, Q. He, F. Wang, J. Fu, D. Bethell, S. McIntosh, C. J. Kiely, G. J. Hutchings, Nature, 2022, 603, 271-275.
[27]	T. Richards, J. H. Harrhy, R. J. Lewis, A. G. R. Howe, G. M. Suldecki, A. Folli, D. J. Morgan, T. E. Davies, E. J. Loveridge, D. A. Crole, J. K. Edwards, P. Gaskin, C. J. Kiely, Q. He, D. M. Murphy, J.-Y. Maillard, S. J. Freakley, G. J. Hutchings, Nat. Catal., 2021, 4, 575-585.
[28]	R. J. Lewis, K. Ueura, X. Liu, Y. Fukuta, T. E. Davies, D. J. Morgan, L. Chen, J. Qi, J. Singleton, J. K. Edwards, S. J. Freakley, C. J. Kiely, Y. Yamamoto, G. J. Hutchings, Science, 2022, 376, 615-620.
[29]	Y. Xu, D. Wu, P. Deng, J. Li, J. Luo, Q. Chen, W. Huang, C. M. Shim, C. Jia, Z. Liu, Y. Shen, X. Tian, Appl. Catal. B, 2022, 308, 121223.
[30]	S. Linic, S. Chavez, R. Elias, Nat. Mater., 2021, 20, 916-924.
[31]	S. Chavez, U. Aslam, S. Linic, ACS Energy Lett., 2018, 3, 1590-1596.
[32]	R. Liu, H.-M. Chen, L.-P. Fang, C. Xu, Z. He, Y. Lai, H. Zhao, D. Bekana, J.-f. Liu, Environ. Sci. Technol., 2018, 52, 4244-4255.
[33]	D. Wu, Z. Li, Z. Qi, S. Hu, R. Long, L. Song, Y. Xiong, ChemNanoMat, 2020, 6, 920-924.
[34]	M. J. Kale, T. Avanesian, P. Christopher, ACS Catal., 2014, 4, 116-128.
[35]	D. Devasia, A. Das, V. Mohan, P. K. Jain, Annu. Rev. Phys. Chem., 2021, 72, 423-443.
[36]	E. Cortés, L. V. Besteiro, A. Alabastri, A. Baldi, G. Tagliabue, A. Demetriadou, P. Narang, ACS Nano, 2020, 14, 16202-16219.
[37]	X. Zhu, Q. Guo, Y. Sun, S. Chen, J.-Q. Wang, M. Wu, W. Fu, Y. Tang, X. Duan, D. Chen, Y. Wan, Nat. Commun., 2019, 10, 1428.
[38]	P. A. P. Nascente, S. G. C. de Castro, R. Landers, G. G. Kleiman, Phys. Rev. B, 1991, 43, 4659-4666.
[39]	M. B. Griffin, A. A. Rodriguez, M. M. Montemore, J. R. Monnier, C. T. Williams, J. W. Medlin, J. Catal., 2013, 307, 111-120.
[40]	R. E. Watson, J. Hudis, M. L. Perlman, Phys. Rev. B, 1971, 4, 4139-4144.
[41]	P. Han, C. Tang, S. Sarina, E. R. Waclawik, A. Du, S. E. Bottle, Y. Fang, Y. Huang, K. Li, H.-Y. Zhu, ACS Catal., 2022, 12, 2280-2289.
[42]	M. J. Kale, T. Avanesian, H. Xin, J. Yan, P. Christopher, Nano Lett., 2014, 14, 5405-5412.
[43]	Q. Xiao, S. Sarina, E. R. Waclawik, H. Zhu, Catal. Sci. Technol., 2021, 11, 2073-2080.
[44]	S. Sarina, E. Jaatinen, Q. Xiao, Y. M. Huang, P. Christopher, J. C. Zhao, H. Y. Zhu, J. Phys. Chem. Lett., 2017, 8, 2526-2534.
[45]	V. G. Rao, U. Aslam, S. Linic, J. Am. Chem. Soc., 2019, 141, 643-647.
[46]	M. M. Sartin, H.-S. Su, X. Wang, B. Ren, J. Chem. Phys., 2020, 153, 170901.
[47]	T. Yoshii, Y. Kuwahara, K. Mori, H. Yamashita, J. Phys. Chem. C, 2019, 123, 24575-24583.
[48]	J.-J. Koo, Z. H. Kim, J. Phys. Chem. Lett., 2022, 13, 3740-3747.
[49]	S. Zhang, C. Chang, Z. Huang, Y. Ma, W. Gao, J. Li, Y. Qu, ACS Catal., 2015, 5, 6481-6488.
[50]	P. Y. Cheng, D. Zhong, A. H. Zewail, Chem. Phys. Lett., 1995, 237, 399-405.
[51]	M. L. Brongersma, N. J. Halas, P. Nordlander, Nat. Nanotechnol., 2015, 10, 25-34.
[52]	S. E. Creutz, K. J. Lotito, G. C. Fu, J. C. Peters, Science, 2012, 338, 647-651.
[53]	M. W. Johnson, K. I. Hannoun, Y. Tan, G. C. Fu, J. C. Peters, Chem. Sci., 2016, 7, 4091-4100.
[54]	C. Uyeda, Y. Tan, G. C. Fu, J. C. Peters, J. Am. Chem. Soc., 2013, 135, 9548-9552.
[55]	R. J. Enemærke, T. B. Christensen, H. Jensen, K. Daasbjerg, J. Chem. Soc. Perkin Trans. 2, 2001, 1620-1630.
[56]	G. Henkelman, A. Arnaldsson, H. Jónsson, Comp. Mater. Sci., 2006, 36, 354-360.
[57]	L. C. Allen, J. Am. Chem. Soc., 1989, 111, 9003-9014.
[58]	Q. Gu, Q. Jia, J. Long, Z. Gao, ChemCatChem, 2019, 11, 669-683.