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Communication

In-situ reconstruction of single-atom Pt on Co3O4 for hydrogenation

Sai Zhang1,2(), Zhaoming Xia3(), Wenbin Li1, You Wang1, Yong Zou1, Mingkai Zhang1, Zhongmiao Gong4, Yi Cui4, Yongquan Qu1 ()
Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710072, China
Research & Development Institute of Northwestern Polytechnical University in Shenzhen, Shenzhen 518057, China
Department of Chemistry, Tsinghua University, Beijing 100084, China
Vacuum Interconnected Nanotech Workstation, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China
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The single-atom Pt on Co3O4 surface reconstructed to form an isolated Pt-Co bimetallic site under hydrogen environment via reducing coordination number of Pt–O. The in-situ reconstructed Pt-Co bimetallic sites delivered a significantly high turnover frequency of 7,448 h−1 with satisfactory selectivity (95.2%) for hydrogenation of cinnamaldehyde into cinnamyl alcohol.

Abstract

Actual chemical states of single-atom metal on reducible supports remain a fiercely debated topic under reactive environments. Herein, we demonstrate that the single-atom Pt on Co3O4 surface undergoes an in-situ reconstruction to form isolated Pt-Co bimetallic sites via reducing coordination number of Pt–O in the presence of hydrogen from both simulations and in-situ X-ray photoelectron spectroscopy. The modified chemical states of Pt greatly promoted H2 activation, thus delivering a significantly high turnover frequency of 7,448 h−1 (19.5 times over Pt nanoparticles on Co3O4) for hydrogenation of cinnamaldehyde. The satisfactory selectivity of 95.2% towards cinnamyl alcohol was ascribed to a tilted adsorption configuration of reactant on the catalyst surface via aldehyde group. We anticipate that the recognitions on in-situ reconstruction of single-atom catalysts (SACs) under the reducing conditions benefit the design of highly-performed hydrogenation catalysts.

Keywords

single-atom catalysis (SACs)coordination environmentPt-Co bimetallic siteshydrogenation

Electronic Supplementary Material

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References

[1]

Lang, R.; Du, X. R.; Huang, Y. K.; Jiang, X. Z.; Zhang, Q.; Guo, Y. L.; Liu, K. P.; Qiao, B. T.; Wang, A. Q.; Zhang, T. Single-atom catalysts based on the metal–oxide interaction. Chem. Rev. 2020, 120, 11986–12043.

Crossref Google Scholar
[2]

Kaiser, S. K.; Chen, Z. P.; Faust Akl, D.; Mitchell, S.; Pérez-Ramírez, J. Single-atom catalysts across the periodic table. Chem. Rev. 2020, 120, 11703–11809.

Crossref Google Scholar
[3]

Hannagan, R. T.; Giannakakis, G.; Flytzani-Stephanopoulos, M.; Sykes, E. C. H. Single-atom alloy catalysis. Chem. Rev. 2020, 120, 12044–12088.

Crossref Google Scholar
[4]

Li, X. N.; Huang, Y. Q.; Liu, B. Catalyst: Single-atom catalysis: Directing the way toward the nature of catalysis. Chem 2019, 5, 2733–2735.

Crossref Google Scholar
[5]

Lin, L. H.; Chen, Z.; Chen, W. X. Single atom catalysts by atomic diffusion strategy. Nano Res. 2021, 14, 4398–4416.

Crossref Google Scholar
[6]

Li, X. Y.; Rong, H. P.; Zhang, J. T.; Wang, D. S.; Li, Y. D. Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance. Nano Res. 2020, 13, 1842–1855.

Crossref Google Scholar
[7]

Ji, S. F.; Chen, Y. J.; Wang, X. L.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Chemical synthesis of single atomic site catalysts. Chem. Rev. 2020, 120, 11900–11955.

Crossref Google Scholar
[8]

Liu, J. C.; Tang, Y.; Wang, Y. G.; Zhang, T.; Li, J. Theoretical understanding of the stability of single-atom catalysts. Natl. Sci. Rev. 2018, 5, 638–641.

Crossref Google Scholar
[9]

Yang, X. F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y.; Zhang, T. Single-atom catalysts: A new frontier in heterogeneous catalysis. Acc. Chem. Res. 2013, 46, 1740–1748.

Crossref Google Scholar
[10]

Qi, K.; Chhowalla, M.; Voiry, D. Single atom is not alone: Metal–support interactions in single-atom catalysis. Mater. Today 2020, 40, 173–192.

Crossref Google Scholar
[11]

Wang, X.; Zhang, Y. W.; Wu, J.; Zhang, Z.; Liao, Q. L.; Kang, Z.; Zhang, Y. Single-atom engineering to ignite 2D transition metal dichalcogenide based catalysis: Fundamentals, progress, and beyond. Chem. Rev. 2022, 122, 1273–1348.

Crossref Google Scholar
[12]

Boyes, E. D.; LaGrow, A. P.; Ward, M. R.; Mitchell, R. W.; Gai, P. L. Single atom dynamics in chemical reactions. Acc. Chem. Res. 2020, 53, 390–399.

Crossref Google Scholar
[13]

Qin, R. X.; Liu, K. L.; Wu, Q. Y.; Zheng, N. F. Surface coordination chemistry of atomically dispersed metal catalysts. Chem. Rev. 2020, 120, 11810–11899.

Crossref Google Scholar
[14]

Samantaray, M. K.; D'Elia, V.; Pump, E.; Falivene, L.; Harb, M.; Ould Chikh, S.; Cavallo, L.; Basset, J. M. The comparison between single atom catalysis and surface organometallic catalysis. Chem. Rev. 2020, 120, 734–813.

Crossref Google Scholar
[15]

Lin, L. L.; Zhou, W.; Gao, R.; Yao, S. Y.; Zhang, X.; Xu, W. Q.; Zheng, S. J.; Jiang, Z.; Yu, Q. L.; Li, Y. W. et al. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts. Nature 2017, 544, 80–83.

Crossref Google Scholar
[16]

Zhang, X.; Zhang, M. T.; Deng, Y. C.; Xu, M. Q.; Artiglia, L.; Wen, W.; Gao, R.; Chen, B. B.; Yao, S. Y.; Zhang, X. C. et al. A stable low-temperature H2-production catalyst by crowding Pt on α-MoC. Nature 2021, 589, 396–401.

Crossref Google Scholar
[17]

Su, C.; Tripathi, M.; Yan, Q. B.; Wang, Z. G.; Zhang, Z. H.; Hofer, C.; Wang, H. Z.; Basile, L.; Su, G.; Dong, M. D. et al. Engineering single-atom dynamics withelectron irradiation. Sci. Adv. 2019, 5, eaav2252.

Crossref Google Scholar
[18]

Daelman, N.; Capdevila-Cortada, M.; López, N. Dynamic charge and oxidation state of Pt/CeO2 single-atom catalysts. Nat. Mater. 2019, 18, 1215–1221.

Crossref Google Scholar
[19]

Nie, L.; Mei, D. H.; Xiong, H. F.; Peng, B.; Ren, Z. B.; Hernandez, X. I. P.; DeLaRiva, A.; Wang, M.; Engelhard, M. H.; Kovarik, L. et al. Activation of surface lattice oxygen in single-atom Pt/CeO2 for low-temperature CO oxidation. Science 2017, 358, 1419–1423.

Crossref Google Scholar
[20]

Ren, Y. J.; Tang, Y.; Zhang, L. L.; Liu, X. Y.; Li, L.; Miao, S.; Sheng Su, D.; Wang, A. Q.; Li, J.; Zhang, T. Unraveling the coordination structure–performance relationship in Pt1/Fe2O3 single-atom catalyst. Nat. Commun. 2019, 10, 4500.

Crossref Google Scholar
[21]

Liu, J.; Bak, J.; Roh, J.; Lee, K. S.; Cho, A.; Han, J. W.; Cho, E. Reconstructing the coordination environment of platinum single-atom active sites for boosting oxygen reduction reaction. ACS Catal. 2021, 11, 466–475.

Crossref Google Scholar
[22]

Yang, J.; Liu, W. G.; Xu, M. Q.; Liu, X. Y.; Qi, H. F.; Zhang, L. L.; Yang, X. F.; Niu, S. S.; Zhou, D.; Liu, Y. F. et al. Dynamic behavior of single-atom catalysts in electrocatalysis: Identification of Cu-N3 as an active site for the oxygen reduction reaction. J. Am. Chem. Soc. 2021, 143, 14530–14539.

Crossref Google Scholar
[23]

Xiao, G. F.; Lu, R. H.; Liu, J. F.; Liao, X. B.; Wang, Z. Y.; Zhao, Y. Coordination environments tune the activity of oxygen catalysis on single atom catalysts: A computational study. Nano Res. 2022, 15, 3073–3081.

Crossref Google Scholar
[24]

Zhou, D.; Zhang, L. L.; Liu, X. Y.; Qi, H. F.; Liu, Q. G.; Yang, J.; Su, Y.; Ma, J. Y.; Yin, J. Z.; Wang, A. Q. Tuning the coordination environment of single-atom catalyst M-N-C towards selective hydrogenation of functionalized nitroarenes. Nano Res. 2022, 15, 519–527.

Crossref Google Scholar
[25]

Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 2011, 3, 634–641.

Crossref Google Scholar
[26]

Zhou, X. M.; Xia, Z. M.; Tian, Z.; Ma, Y. Y.; Qu, Y. Q. Ultrathin porous Co3O4 nanoplates as highly efficient oxygen evolution catalysts. J. Mater. Chem. A 2015, 3, 8107–8114.

Crossref Google Scholar
[27]

Fickenscher, G.; Hohner, C.; Xu, T.; Libuda, J. Adsorption of D2O and CO on Co3O4(111): Water stabilizes coadsorbed CO. J. Phys. Chem. C 2021, 125, 26785–26792.

Crossref Google Scholar
[28]

Ferstl, P.; Mehl, S.; Arman, M. A.; Schuler, M.; Toghan, A.; Laszlo, B.; Lykhach, Y.; Brummel, O.; Lundgren, E.; Knudsen, J. et al. Adsorption and activation of CO on Co3O4(111) thin films. J. Phys. Chem. C 2015, 119, 16688–16699.

Crossref Google Scholar
[29]

Jiang, D.; Yao, Y. G.; Li, T. Y.; Wan, G.; Pereira-Hernández, X. I.; Lu, Y. B.; Tian, J. S.; Khivantsev, K.; Engelhard, M. H.; Sun, C. J. et al. Tailoring the local environment of platinum in single-atom Pt1/CeO2 catalysts for robust low-temperature CO oxidation. Angew. Chem., Int. Ed. 2021, 60, 26054–26062.

Crossref Google Scholar
[30]

Lu, Y. B.; Zhou, S. L.; Kuo, C. T.; Kunwar, D.; Thompson, C.; Hoffman, A. S.; Boubnov, A.; Lin, S.; Datye, A. K.; Guo, H. et al. Unraveling the intermediate reaction complexes and critical role of support-derived oxygen atoms in CO oxidation on single-atom Pt/CeO2. ACS Catal. 2021, 11, 8701–8715.

Crossref Google Scholar
[31]

Li, Y. Y.; Kottwitz, M.; Vincent, J. L.; Enright, M. J.; Liu, Z. Y.; Zhang, L. H.; Huang, J. H.; Senanayake, S. D.; Yang, W. C. D.; Crozier, P. A. et al. Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction. Nat. Commun. 2021, 12, 914.

Crossref Google Scholar
[32]

Chen, H. Y. T.; Tosoni, S.; Pacchioni, G. Hydrogen adsorption, dissociation, and spillover on Ru10 clusters supported on anatase TiO2 and tetragonal ZrO2(101) surfaces. ACS Catal. 2015, 5, 5486–5495.

Crossref Google Scholar
[33]

Zhang, S.; Xia, Z. M.; Zhang, M. K.; Zou, Y.; Shen, H. D.; Li, J. Y.; Chen, X.; Qu, Y. Q. Boosting selective hydrogenation through hydrogen spillover on supported-metal catalysts at room temperature. Appl. Catal. B:Environ. 2021, 297, 120418.

Crossref Google Scholar
[34]

Sihag, A.; Xie, Z. L.; Thang, H. V.; Kuo, C. L.; Tseng, F. G.; Dyer, M. S.; Chen, H. Y. T. DFT insights into comparative hydrogen adsorption and hydrogen spillover mechanisms of Pt4/graphene and Pt4/anatase(101) surfaces. J. Phys. Chem. C 2019, 123, 25618–25627.

Crossref Google Scholar
[35]

Luneau, M.; Lim, J. S.; Patel, D. A.; Sykes, E. C. H.; Friend, C. M.; Sautet, P. Guidelines to achieving high selectivity for the hydrogenation of α, β-unsaturated aldehydes with bimetallic and dilute alloy catalysts: A review. Chem. Rev. 2020, 120, 12834–12872.

Crossref Google Scholar
[36]

Wang, X. F.; Liang, X. H.; Geng, P.; Li, Q. B. Recent advances in selective hydrogenation of cinnamaldehyde over supported metal-based catalysts. ACS Catal. 2020, 10, 2395–2412.

Crossref Google Scholar
[37]

Lan, X. C.; Wang, T. F. Highly selective catalysts for the hydrogenation of unsaturated aldehydes: A review. ACS Catal. 2020, 10, 2764–2790.

Crossref Google Scholar
Nano Research
Volume 16 Issue 5,
May 2023
Pages 6507-6511
DOI: 10.1007/s12274-022-5279-1
Cite this article:
Zhang S, Xia Z, Li W, et al. In-situ reconstruction of single-atom Pt on Co3O4 for hydrogenation. Nano Research, 2023, 16(5): 6507-6511. https://doi.org/10.1007/s12274-022-5279-1
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