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Research Article

Hydriding Pd cocatalysts: An approach to giant enhancement on photocatalytic CO2 reduction into CH4

Yuzhen Zhu1,§, Chao Gao2,§, Song Bai1(), Shuangming Chen2, Ran Long2, Li Song2, Zhengquan Li1(), Yujie Xiong2()
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Life Sciences, Institute of Physical and Chemistry Zhejiang Normal UniversityJinhua 321004 China
Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory University of Science and Technology of ChinaHefei 230026 China

§ Yuzhen Zhu and Chao Gao contributed equally to this work.

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Abstract

Photocatalytic reduction of CO2 into high value-added CH4 is a promising solution for energy and environmental crises. Integrating semiconductors with cocatalysts can improve the activities for photocatalytic CO2 reduction; however, most metal cocatalysts mainly produce CO and H2. Herein, we report a cocatalyst hydridation approach for significantly enhancing the photocatalytic reduction of CO2 into CH4. Hydriding Pd cocatalysts into PdH0.43 played a dual role in performance enhancement. As revealed by our isotopic labeling experiments, the PdH0.43 hydride cocatalysts reduced H2 evolution, which suppressed the H2 production and facilitated the conversion of the CO intermediate into the final product: CH4. Meanwhile, hydridation promoted the electron trapping on the cocatalysts, improving the charge separation. This approach increased the photocatalytic selectivity in CH4 production from 3.2% to 63.6% on Pd{100} and from 15.6% to 73.4% on Pd{111}. The results provide insights into photocatalytic mechanism studies and introduce new opportunities for designing materials towards photocatalytic CO2 conversion.

Keywords

photocatalysiscocatalystpalladium hydridecarbon dioxidemethane

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References

1

Roy, S. C.; Varghese, O. K.; Paulose, M.; Grimes, C. A. Toward solar fuels: Photocatalytic conversion of carbon dioxide to hydrocarbons. ACS Nano 2010, 4, 1259–1278.

Crossref Google Scholar
2

Habisreutinger, S. N.; Schmidt-Mende, L.; Stolarczyk, J. K. Photocatalytic reduction of CO2 on TiO2 and other semicon­ductors. Angew. Chem., Int. Ed. 2013, 52, 7372–7408.

Crossref Google Scholar
3

Tu, W. G.; Zhou, Y.; Zou, Z. G. Photocatalytic conversion of CO2 into renewable hydrocarbon fuels: State-of-the-art accomplishment, challenges, and prospects. Adv. Mater. 2014, 26, 4607–4626.

Crossref Google Scholar
4

White, J. L.; Baruch, M. F.; Pander, J. E., III; Hu, Y.; Fortmeyer, I. C.; Park, J. E.; Zhang, T.; Liao, K.; Gu, J.; Yan, Y. et al. Light-driven heterogeneous reduction of carbon dioxide: Photocatalysts and photoelectrodes. Chem. Rev. 2015, 115, 12888–12935.

Crossref Google Scholar
5

Inoue, T.; Fujishima, A.; Konishi, S.; Honda, K. Photoelec­trocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders. Nature 1979, 277, 637–638.

Crossref Google Scholar
6

Yu, J. G.; Low, J. X.; Xiao, W.; Zhou, P.; Jaroniec, M. Enhanced photocatalytic CO2-reduction activity of anatase TiO2 by coexposed {001} and {101} facets. J. Am. Chem. Soc. 2014, 136, 8839–8842.

Crossref Google Scholar
7

Wang, W. N.; An, W. J.; Ramalingam, B.; Mukherjee, S.; Niedzwiedzki, D. M.; Gangopadhyay, S.; Biswas, P. Size and structure matter: Enhanced CO2 photoreduction efficiency by size-resolved ultrafine Pt nanoparticles on TiO2 single crystals. J. Am. Chem. Soc. 2012, 134, 11276–11281.

Crossref Google Scholar
8

Liu, Q.; Zhou, Y.; Kou, J. H.; Chen, X. Y.; Tian, Z. P.; Gao, J.; Yan, S. C.; Zou, Z. G. High-yield synthesis of ultralong and ultrathin Zn2GeO4 nanoribbons toward improved photocatalytic reduction of CO2 into renewable hydrocarbon fuel. J. Am. Chem. Soc. 2010, 132, 14385–14387.

Crossref Google Scholar
9

Li, P.; Zhou, Y.; Zhao, Z. Y.; Xu, Q. F.; Wang, X. Y.; Xiao, M.; Zou, Z. G. Hexahedron prism-anchored octahedronal CeO2: Crystal facet-based homojunction promoting efficient solar fuel synthesis. J. Am. Chem. Soc. 2015, 137, 9547–9550.

Crossref Google Scholar
10

Xi, G. C.; Ouyang, S. X.; Li, P.; Ye, J. H.; Ma, Q.; Su, N.; Bai, H.; Wang, C. Ultrathin W18O49 nanowires with diameters below 1 nm: Synthesis, near-infrared absorption, photolumine­scence, and photochemical reduction of carbon dioxide. Angew. Chem., Int. Ed. 2012, 51, 2395–2399.

Crossref Google Scholar
11

Iizuka, K.; Wato, T.; Miseki, Y.; Saito, K.; Kudo, A. Photo­catalytic reduction of carbon dioxide over Ag cocatalyst-loaded ALa4Ti4O15 (A = Ca, Sr, and Ba) using water as a reducing reagent. J. Am. Chem. Soc. 2011, 133, 20863–20868.

Crossref Google Scholar
12

Bai, S.; Jiang, J.; Zhang, Q.; Xiong, Y. J. Steering charge kinetics in photocatalysis: Intersection of materials syntheses, characterization techniques and theoretical simulations. Chem. Soc. Rev. 2015, 44, 2893–2939.

Crossref Google Scholar
13

Zhai, Q. G.; Xie, S. J.; Fan, W. Q.; Zhang, Q. H.; Wang, Y.; Deng, W. P.; Wang, Y. Photocatalytic conversion of carbon dioxide with water into methane: Platinum and copper(Ⅰ) oxide co-catalysts with a core–shell structure. Angew. Chem., Int. Ed. 2013, 52, 5776–5779.

Crossref Google Scholar
14

Bai, S.; Wang, X. J.; Hu, C. Y.; Xie, M. L.; Jiang, J.; Xiong, Y. J. Two-dimensional g-C3N4: An ideal platform for examining facet selectivity of metal co-catalysts in photo­catalysis. Chem. Commun. 2014, 50, 6094–6097.

Crossref Google Scholar
15

Neaţu, S.; Maciá-Agulló, J. A.; Concepción, P.; Garcia, H. Gold–copper nanoalloys supported on TiO2 as photocatalysts for CO2 reduction by water. J. Am. Chem. Soc. 2014, 136, 15969–15976.

Crossref Google Scholar
16

Varghese, O. K.; Paulose, M.; LaTempa, T. J.; Grimes, C. A. High-rate solar photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels. Nano Lett. 2009, 9, 731–737.

Crossref Google Scholar
17

Yang, J. H.; Wang, D.; Han, H. X.; Li, C. Roles of cocatalysts in photocatalysis and photoelectrocatalysis. Acc. Chem. Res. 2013, 46, 1900–1909.

Crossref Google Scholar
18

Marszewski, M.; Cao, S. W.; Yu, J. G.; Jaroniec, M. Semiconductor-based photocatalytic CO2 conversion. Mater. Horiz. 2015, 2, 261–278.

Crossref Google Scholar
19

Sarkar, A.; Gracia-Espino, E.; Wågberg, T.; Shchukarev, A.; Mohl, M.; Rautio, A. R.; Pitkänen, O.; Sharifi, T.; Kordas, K.; Mikkola, J. P. Photocatalytic reduction of CO2 with H2O over modified TiO2 nanofibers: Understanding the reduction pathway. Nano Res. 2016, 9, 1956–1968.

Crossref Google Scholar
20

Tan, L. L.; Ong, W. J.; Chai, S. P.; Mohamed, A. R. Noble metal modified reduced graphene oxide/TiO2 ternary nanostructures for efficient visible-light-driven photoreduction of carbon dioxide into methane. Appl. Catal. B: Environ. 2015, 166–167, 251–259.

Crossref Google Scholar
21

Zhang, X. J.; Han, F.; Shi, B.; Farsinezhad, S.; Dechaine, G. P.; Shankar, K. Photocatalytic conversion of diluted CO2 into light hydrocarbons using periodically modulated multiwalled nanotube arrays. Angew. Chem., Int. Ed. 2012, 51, 12732–12735.

Crossref Google Scholar
22

Han, X. G.; Kuang, Q.; Jin, M. S.; Xie, Z. X.; Zheng, L. S. Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties. J. Am. Chem. Soc. 2009, 131, 3152–3153.

Crossref Google Scholar
23

Ressler, T. WinXAS: A program for X-ray absorption spectroscopy data analysis under MS-Windows. J. Synchrotron Rad. 1998, 5, 118–122.

Crossref Google Scholar
24

Ankudinov, A. L.; Ravel, B.; Rehr, J. J.; Conradson, S. D. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure. Phys. Rev. B 1998, 58, 7565–7576.

Crossref Google Scholar
25

Zhao, Z. P.; Huang, X. Q.; Li, M. F.; Wang, G. M.; Lee, C.; Zhu, E. B.; Duan, X. F.; Huang, Y. Synthesis of stable shape-controlled catalytically active β-palladium hydride. J. Am. Chem. Soc. 2015, 137, 15672–15675.

Crossref Google Scholar
26

Di Vece, M.; Grandjean, D.; Van Bael, M. J.; Romero, C. P.; Wang, X.; Decoster, S.; Vantomme, A.; Lievens, P. Hydrogen- induced ostwald ripening at room temperature in a Pd nanocluster film. Phys. Rev. Lett. 2008, 100, 236105.

Crossref Google Scholar
27

Davis, R. J.; Landry, S. M.; Horsley, J. A.; Boudart, M. X-ray-absorption study of the interaction of hydrogen with clusters of supported palladium. Phys. Rev. B 1989, 39, 10580–10583.

Crossref Google Scholar
28

Watari, N.; Ohnishi, S.; Ishii, Y. Hydrogen storage in Pd clusters. J. Phys. : Condens. Matter 2000, 12, 6799–6823.

Crossref Google Scholar
29

Kato, S.; Matam, S. K.; Kerger, P.; Bernard, L.; Battaglia, C.; Vogel, D.; Rowerder, M.; Züttel, A. The origin of the catalytic activity of a metal hydride in CO2 reduction. Angew. Chem., Int. Ed. 2016, 55, 6028–6032.

Crossref Google Scholar
30

Zhang, S.; Kang, P.; Bakir, M.; Lapides, A. M.; Dares, C. J.; Meyer, T. J. Polymer-supported CuPd nanoalloy as a synergistic catalyst for electrocatalytic reduction of carbon dioxide to methane. Proc. Natl. Acad. Sci. USA 2015, 112, 15809–15814.

Crossref Google Scholar
31

Park, H. A.; Choi, J. H.; Choi, K. M.; Lee, D. K.; Kang, J. K. Highly porous gallium oxide with a high CO2 affinity for the photocatalytic conversion of carbon dioxide into methane. J. Mater. Chem. 2012, 22, 5304–5307.

Crossref Google Scholar
32

Liu, H. M.; Li, M.; Dao, T. D.; Liu, Y. Y.; Zhou, W.; Liu, L. Q.; Meng, X. G.; Nagao, T.; Ye, J. H. Design of PdAu alloy plasmonic nanoparticles for improved catalytic performance in CO2 reduction with visible light irradiation. Nano Energy 2016, 26, 398–404.

Crossref Google Scholar
Nano Research
Volume 10 Issue 10,
October 2017
Pages 3396-3406
DOI: 10.1007/s12274-017-1552-0
Cite this article:
Zhu Y, Gao C, Bai S, et al. Hydriding Pd cocatalysts: An approach to giant enhancement on photocatalytic CO2 reduction into CH4. Nano Research, 2017, 10(10): 3396-3406. https://doi.org/10.1007/s12274-017-1552-0
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