Synergy Effect of Pd Nanoparticles and Oxygen Vacancies for Enhancing TiO2 Photocatalytic CO2 Reduction

doi:10.15541/jim20230170

Abstract

Abstract:

In this study, one-dimensional single-crystal TiO₂ nanobelt arrays with surface oxygen vacancies were constructed by Pd-catalyzed oxygen reduction method in anoxic environment to address the problems of insufficient surface active sites and slow reaction kinetics of TiO₂, low yield and poor selectivity of hydrocarbons in CO₂ reduction products. The effects of surface oxygen vacancies and hydrogen spillover of Pd on the separation and transport of photogenerated carrier and the selectivity of reduction product were investigated from morphological structure, carrier behavior and photocatalytic performance. With high CO₂ reduction activity of Pd-Ov-TNB, yields of CH₄, C₂H₆ and C₂H₄ are 40.8, 32.09 and 3.09 µmol·g^-1·h^-1, respectively, and selectivity of hydrocarbons is as high as 84.52%, showing great potential in C-C coupling. Its excellent photocatalytic activity is attributed to the one-dimensional single-crystal nanobelt structure that increases the active specific surface area and crystallinity of the material, provides more active sites for the CO₂ reduction and accelerates the segregated transport of photogenerated charges. Meanwhile, the oxygen vacancies enhance the surface accumulation of photogenerated charges, providing an electron-rich environment for CO₂ reduction. In addition, Pd nanoparticles increase concentration of H* in the reaction system, and then transfer H* to active sites of CO₂ adsorption on the catalyst surface through the hydrogen spillover effect, promoting the hydrogenation of reaction intermediates. Comprehensive advantages of Pd-nanoparticals contribute to the efficient conversion of CO₂ to hydrocarbons.

Key words: oxygen vacancies, TiO₂ nanobelt, hydrogen spillover, photocatalytic CO₂ reduction

CLC Number:

TQ174

JIA Xin, LI Jinyu, DING Shihao, SHEN Qianqian, JIA Husheng, XUE Jinbo. Synergy Effect of Pd Nanoparticles and Oxygen Vacancies for Enhancing TiO₂ Photocatalytic CO₂ Reduction[J]. Journal of Inorganic Materials, 2023, 38(11): 1301-1308.

Figures/Tables 8

Fig. 1 (a-c) SEM images, (e-g)EDS spectra, (h) XRD patterns and (i) EPR spectra of (a, e) Pd-Ov-TNB, (b, f) Pd-TNB and (c, g) Ov-TNB; (d) Analytical mapping of EDS point of square area in (a)

Fig. 2 (a) TEM image of Pd-Ov-TNB; (b) HRTEM image of rectanglar area in Fig.(a); (c) HRTEM image and (d) SAED pattern of the nanobelt

Fig. 3 (a) XPS full survey spectra of Pd-Ov-TNB, Ov-TNB and Pd-TNB, with corresponding high-resolution XPS spectra of (b) O1s, (c) Ti2p and (d) Pd3d

Fig. 4 (a) Photocatalytic CO2 reduction performance of Pd-Ov-TNB, Ov-TNB and Pd-TNB and (b) recycling curves of Pd-Ov-TNB for photocatalytic CO2 reduction Colorful figures are available on website

Table 1 Activities and selectivities for photocatalytic reduction of CO2 over the obtained samples

Photocatalyst	Productivity/(μmol·g^-1·h^-1)					Selectivity for hydrocarbon products/%
Photocatalyst	CO	CH₄	C₂H₆	C₂H₄	H₂	Selectivity for hydrocarbon products/%
Pd-Ov-TNB	70.7	40.8	32.09	3.09	3.69	84.52
Pd-TNB	80.21	19.92	10.71	2.02	10.04	64.88
Ov-TNB	113.58	15.32	2.071	0	4.25	39.14

Table 2 Photocatalytic performance of CO2 reduction of photocatalysts in literature

Photocatalyst	Productivity / (μmol·g^-1·h^-1)					Selectivity for hydrocarbon products/%	Ref.
Photocatalyst	CO	CH₄	C₂H₆	C₂H₄	H₂	Selectivity for hydrocarbon products/%	Ref.
Pd-Ov-TNB	70.7	40.8	32.09	3.087	3.69	84.52	This work
1%Ru-TiO_2-_x	5.06	31.36	-	-	-	96.12	[24]
In-TiO₂	81	244	2.78	0.06	-	92.48	[25]
In-TiO₂/g-C₃N₄	2.32	7.31	-	1.41	-	94.20	[26]
Au₆Pd₁/TiO₂	10.9	12.7	0.8	0.7	-	84.75	[27]
Cu^δ⁺/CeO₂-TiO₂	3.47	1.52	-	4.51	-	90.52	[28]
Pd/Mn-TiO₂	17.88	5.51	1.32	-	-	55.21	[29]
PdNRs-TiO₂	12.6	3.0	-	-	8.826	35.90	[30]
Ti₃C₂/P25	11.74	16.61	-	-	35.0	58.70	[31]
ZXN-TC	1296.4	98.11	41.07	2.25	-	34.85	[32]

Fig. 5 (a) UV-Vis DRS spectra, (b) PL emission spectra, (c) SPV spectra, (d) I-t curves, (e) EIS plots, and (f) Mott-Schottky plots of Pd-Ov-TNB, Ov-TNB and Pd-TNB

Fig. 6 Photocatalytic CO2 reduction mechanism of Pd-Ov-TNB

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Synergy Effect of Pd Nanoparticles and Oxygen Vacancies for Enhancing TiO₂ Photocatalytic CO₂ Reduction

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