Pd纳米颗粒协同氧空位增强TiO2光催化CO2还原性能

doi:10.15541/jim20230170

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1301-1308.DOI: 10.15541/jim20230170 CSTR: 32189.14.10.15541/jim20230170

所属专题：【能源环境】光催化(202412)；【能源环境】CO2绿色转换(202506)

Pd纳米颗粒协同氧空位增强TiO₂光催化CO₂还原性能

贾鑫¹^,²(), 李晋宇¹^,², 丁世豪¹^,², 申倩倩¹^,², 贾虎生¹^,², 薛晋波¹^,²()

1.太原理工大学 1. 新材料界面科学与工程教育部重点实验室
2.材料科学与工程学院, 太原 030024

收稿日期:2023-04-06 修回日期:2023-06-26 出版日期:2023-07-17 网络出版日期:2023-07-17
通讯作者: 薛晋波, 副教授. E-mail: xuejinbo@tyut.edu.cn
作者简介:贾鑫(1995-), 男, 硕士研究生. E-mail: 547623834@qq.com
基金资助:
国家自然科学基金(62004137);国家自然科学基金(21878257);国家自然科学基金(21978196);山西省自然科学基金(20210302123102);山西省重点研发计划项目(201803D421079);山西省高等学校科技创新项目(2019L0156);山西省回国留学人员科研资助项目(2020-050)

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

JIA Xin¹^,²(), LI Jinyu¹^,², DING Shihao¹^,², SHEN Qianqian¹^,², JIA Husheng¹^,², XUE Jinbo¹^,²()

1. Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, China
2. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Received:2023-04-06 Revised:2023-06-26 Published:2023-07-17 Online:2023-07-17
Contact: XUE Jinbo, associate professor. E-mail: xuejinbo@tyut.edu.cn
About author:About author: JIA Xin (1995-), male, Master candidate. E-mail: 547623834@qq.com
Supported by:
National Natural Science Foundation of China(62004137);National Natural Science Foundation of China(21878257);National Natural Science Foundation of China(21978196);Natural Science Foundation of Shanxi Province(20210302123102);Key Research and Development Program of Shanxi Province(201803D421079);Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2019L0156);Shanxi Scholarship Council of China(2020-050)

摘要/Abstract

摘要：

针对TiO₂表面活性位点不足、反应动力学缓慢、CO₂还原产物中碳氢化合物的产率低以及选择性差等问题, 研究通过Pd催化氧还原法在缺氧环境中构筑了具有表面氧空位的一维单晶TiO₂纳米带阵列(Pd-Ov-TNB)。通过形貌结构、载流子行为及光催化性能分析, 探究了表面氧空位和Pd的氢溢流效应对光生载流子分离传输及还原产物选择性的影响。结果表明, Pd-Ov-TNB的CO₂还原活性强, 产物中CH₄、C₂H₆和C₂H₄的产率分别为40.8、32.09和3.09 µmol·g^-1·h^-1, 碳氢化合物的选择性高达84.52%, 在C-C偶联方面展现出巨大的潜力。其一维单晶纳米带结构提高了材料的活性比表面积和结晶度, 为CO₂还原反应提供了更多的活性位点, 并加速载流子的分离传输。同时, 氧空位增强了光生电荷的表面积累, 为CO₂还原提供了富电子环境。此外, Pd纳米颗粒提高反应体系中H*的浓度, 并通过氢溢流效应将H*转移到催化剂表面吸附CO₂的活性位点, 促进反应中间产物氢化。各种优势共同作用促使CO₂向碳氢化合物高效转化。

关键词: 氧空位, TiO₂纳米带, 氢溢流, 光催化还原CO₂

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

中图分类号:

TQ174

贾鑫, 李晋宇, 丁世豪, 申倩倩, 贾虎生, 薛晋波. Pd纳米颗粒协同氧空位增强TiO₂光催化CO₂还原性能[J]. 无机材料学报, 2023, 38(11): 1301-1308.

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.

图/表 8

图1 (a, e) Pd-Ov-TNB、(b, f) Pd-TNB和(c, g) Ov-TNB的(a~c)SEM照片、(e~g)EDS图谱、(h) XRD图谱和(i) EPR图谱; (d) Pd-Ov-TNB(a)中虚线框位置的EDS点分析图谱

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)

图2 (a) Pd-Ov-TNB的TEM照片; (b) 图(a)中方框部位的HRTEM照片; (c) 纳米带部位的HRTEM照片; (d) 纳米带的选区电子衍射图

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

图3 (a) Pd-Ov-TNB、Ov-TNB以及Pd-TNB的XPS全谱; (b) O1s、(c) Ti2p和(d) Pd3d的高分辨XPS图谱

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

图4 (a) Pd-Ov-TNB、Ov-TNB和Pd-TNB的光催化还原CO2性能和(b) Pd-Ov-TNB光催化还原CO2的循环曲线

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

表1 样品的光催化还原CO2的活性和选择性

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

表2 文献报道的光催化剂的CO2还原性能

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]

图5 Pd-Ov-TNB、Ov-TNB和Pd-TNB的(a) UV-Vis DRS光谱图、(b) PL光谱图、(c) SPV光谱图、(d) I-t曲线、(e) EIS阻抗谱图和(f) 莫特−肖特基曲线

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

图6 Pd-Ov-TNB光催化还原CO2机制

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

参考文献 35

[1]	SHEN Q Q, XUE J B, LI Y, et al. Construction of CdSe polymorphic junctions with coherent interface for enhanced photoelectrocatalytic hydrogen generation. Applied Catalysis B: Environmental, 2021, 282: 119552. DOI URL
[2]	LI C J, XUE Y, ZHOU X X, et al. BiZn_x/Si photocathode: preparation and CO₂ reduction performance. Journal of Inorganic Materials, 2022, 37(10): 1093. DOI URL
[3]	XU S Z, CARTER E A. Theoretical insights into heterogeneous (photo) electrochemical CO₂ reduction. Chemical Reviews, 2019, 119(11): 6631. DOI URL
[4]	PANG Q H, LIAO G F, HU X Y, et al. Porous bamboo charcoal/ TiO₂ nanocomposites: preparation and photocatalytic property. Journal of Inorganic Materials, 2019, 34(2): 219. DOI URL
[5]	HAO L, HUANG H W, ZHANG Y H, et al. Oxygen vacant semiconductor photocatalysts. Advanced Functional Materials, 2021, 31(25): 2100919. DOI URL
[6]	VERBRUGGEN A W, MASSCHAELE K, MOORTGAT E, et al. Factors driving the activity of commercial titanium dioxide powders towards gas phase photocatalytic oxidation of acetaldehyde. Catalysis Science & Technology, 2012, 2: 2311.
[7]	KERI Q, KOCSIS E, KARAJZ D A, et al. Photocatalytic crystalline and amorphous TiO₂ nanotubes prepared by electrospinning and atomic layer deposition. Molecules, 2021, 26(19): 5917. DOI URL
[8]	BUNSHO O, YOSHIMASA O, SEIICHI N. Photocatalytic activity of amorphous anatase mixture of titanium(IV) oxide particles suspended in aqueous solutions. Journal of Physical Chemistry B, 1997, 101(19): 3746. DOI URL
[9]	BELLARDITA M, PAOLA A D, MEGNA B, et al. Absolute crystallinity and photocatalytic activity of brookite TiO₂ samples. Applied Catalysis B: Environmental, 2017, 201: 150. DOI URL
[10]	WANG S Q, ZHANG Z L, HUO W Y, et al. Preferentially oriented Ag-TiO₂ nanotube array film: an efficient visible-light-driven photocatalyst. Journal of Hazardous Materials, 2020, 399: 123016. DOI URL
[11]	DENG Z S, JI J H, XING M Y, et al. The role of oxygen defects in metal oxides for CO₂ reduction. Nanoscale Advances, 2020, 2: 4986. DOI URL
[12]	JIANG W B, LOH H Y, LOW B Q L, et al. Role of oxygen vacancy in metal oxides for photocatalytic CO₂ reduction. Applied Catalysis B: Environmental, 2023, 321: 122079. DOI URL
[13]	JI Y F, LUO Y. New mechanism for photocatalytic reduction of CO₂ on the anatase TiO₂(101) surface: the essential role of oxygen vacancy. Journal of the American Chemical Society, 2016, 138(49): 15896. DOI URL
[14]	ZHANG T, LOW J X, YU J G, et al. A blinking mesoporous TiO_2-_x composed of nanosized anatase with unusually long-lived trapped charge carriers. Angewandte Chemie International Edition, 2020, 59(35): 15000. DOI URL
[15]	GAO J Q, SHEN Q Q, GUAN R F, et al. Oxygen vacancy self- doped black TiO₂ nanotube arrays by aluminothermic reduction for photocatalytic CO₂ reduction under visible light illumination. Journal of CO₂ Utilization, 2020, 35: 205.
[16]	GAO J Q, XUE J B, JIA S F, et al. Self-doping surface oxygen vacancy-induced lattice strains for enhancing visible light-driven photocatalytic H₂ evolution over black TiO₂. ACS Applied Materials & Interfaces, 2021, 13(16): 18758.
[17]	WANG Y Y, QU Y, QU B H, et al. Construction of six-oxygen- coordinated single Ni sites on g-C₃N₄ with boron-oxo species for photocatalytic water-activation-induced CO₂ reduction. Advanced Materials, 2021, 33(48): 2105482. DOI URL
[18]	WANG Z Q, ZHU J C, ZU X L, et al. Selective CO₂ photoreduction to CH₄ via Pd^δ⁺-assisted hydrodeoxygenation over CeO₂ nanosheets. Angewandte Chemie International Edition, 2022, 61(30): e202203249. DOI URL
[19]	ZHANG W J, SHEN Q Q, XUE J B, et al. Preparation and photoelectrochemical water oxidation of hematite nanobelts containing highly ordered oxygen vacancies. Journal of Inorganic Materials, 2021, 36(12): 1290. DOI
[20]	WANG L L, YANG T, PENG L J, et al. Dual transfer channels of photo-carriers in 2D/2D/2D sandwich-like ZnIn₂S₄/g-C₃N₄/Ti₃C₂ MXene S-scheme/Schottky heterojunction for boosting photocatalytic H₂ evolution. Chinese Journal of Catalysis, 2022, 43: 2720. DOI URL
[21]	CAI S C, CHEN J, LI Q, et al. Enhanced photocatalytic CO₂ reduction with photothermal effect by cooperative effect of oxygen vacancy and Au cocatalyst. ACS Applied Materials & Interfaces, 2021, 13(12): 14221.
[22]	XIANG Q J, LÜ K L, YU J G. Pivotal role of fluorine in enhanced photocatalytic activity of anatase TiO₂ nanosheets with dominant (001) facets for the photocatalytic degradation of acetone in air. Applied Catalysis B: Environmental, 2010, 96(3/4): 557. DOI URL
[23]	MANIVANNAN S, AN S, JEONG J, et al. Hematite/M (M=Au, Pd) catalysts derived from a double-hollow Prussian blue microstructure: simultaneous catalytic reduction of o- and p-nitrophenols. ACS Applied Materials & Interfaces, 2020, 12(15): 17557.
[24]	ZHOU Y M, ZHANG Q X, SHI X L, et al. Photocatalytic reduction of CO₂ into CH₄ over Ru-doped TiO₂: synergy of Ru and oxygen vacancies. Journal of Colloid and Interface Science, 2022, 608: 2809. DOI URL
[25]	TAHIR M, AMIN N S. Indium-doped TiO₂ nanoparticles for photocatalytic CO₂ reduction with H₂O vapors to CH₄. Applied Catalysis B: Environmental, 2015, 162: 98. DOI URL
[26]	PARK J, LIU H, PIAO G X, et al. Synergistic conversion of CO₂ into C₁ and C₂ gases using hybrid In-doped TiO₂ and g-C₃N₄ photocatalysts. Chemical Engineering Journal, 2022, 437: 135388. DOI URL
[27]	CHEN Q, CHEN X J, FANG M L, et al. Photo-induced Au-Pd alloying at TiO₂ {101} facets enables robust CO₂ photocatalytic reduction into hydrocarbon fuels. Journal of Materials Chemistry A, 2019, 7: 1334. DOI URL
[28]	WANG T, CHEN L, CHEN C, et al. Engineering catalytic interfaces in Cu^δ⁺/CeO₂-TiO₂ photocatalysts forsynergistically boosting CO₂ reduction to ethylene. ACS Nano, 2022, 16(2): 2306. DOI URL
[29]	CAO C, YAN Y B, YU Y L, et al. Modification of Pd and Mn on the surface of TiO₂ with enhanced photocatalytic activity for photoreduction of CO₂ into CH₄. The Journal of Physical Chemistry C, 2017, 121(1): 270. DOI URL
[30]	ZHU Y Z, XU Z X, JIANG W Y, et al. Engineering on the edge of Pd nanosheet cocatalysts for enhanced photocatalytic reduction of CO₂ to fuels. Journal of Materials Chemistry A, 2017, 5: 2619. DOI URL
[31]	YE M H, WANG X, LIU E Z, et al. Boosting the photocatalytic activity of P25 for carbon dioxide reduction by using a surface- alkalinized titanium carbide MXene as cocatalyst. ChemSusChem, 2018, 11(10): 1606. DOI URL
[32]	NI B X, JIANG H, GUO W Y, et al. Tailoring the oxidation state of metallic TiO through Ti³⁺/Ti²⁺ regulation for photocatalytic conversion of CO₂ to C₂H₆. Applied Catalysis B: Environmental, 2022, 307: 121141. DOI URL
[33]	ASCHAUER U, PFENNINGER R, SELBACH S M, et al. Strain- controlled oxygen vacancy formation and ordering in CaMnO₃. Physical Review B, 2013, 88(5): 054111. DOI URL
[34]	LIU Q Q, HE X D, PENG J J, et al. Hot-electron-assisted S- scheme heterojunction of tungsten oxide/graphitic carbon nitride for broad-spectrum photocatalytic H₂ generation. Chinese Journal of Catalysis, 2021, 42(9): 1478. DOI URL
[35]	YANG T, DENG P K, WANG L L, et al. Simultaneous photocatalytic oxygen production and hexavalent chromium reduction in Ag₃PO₄/C₃N₄ S-scheme heterojunction. Chinese Journal of Structural Chemistry, 2022, 41(6): 2206023.

Pd纳米颗粒协同氧空位增强TiO₂光催化CO₂还原性能

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

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