Ag与Ag2O协同增强TiO2光催化制氢性能的研究

doi:10.15541/jim20190460

摘要/Abstract

摘要：

本研究采用两步法制备了电子助剂Ag和界面活性位点Ag₂O共修饰的高效TiO₂光催化剂(TiO₂/Ag-Ag₂O): 首先用光沉积法将Ag负载在TiO₂表面(TiO₂/Ag), 再经过低温煅烧法使部分Ag原位生成Ag₂O。紫外光照射TiO₂时, 激发产生的电子被助剂Ag捕获后快速传输到Ag₂O上, 电子把Ag₂O界面产氢活性位点从溶液中所捕获的氢离子还原成氢气, Ag和Ag₂O的协同作用加快了TiO₂上光生电子的转移和界面产氢反应, 从而提高了TiO₂/Ag-Ag₂O制氢性能。在300 ℃煅烧温度下制备的TiO₂/Ag-Ag₂O光催化剂制氢速率最高, 达到75.20 μmol/h, 分别是TiO₂(3.59 μmol/h)和TiO₂/Ag(41.13 μmol/h)的21.0倍和1.8倍。本研究为光催化制氢材料的设计和制备提供了有益的参考。

关键词: TiO₂, 电子助剂, 界面活性位点, 协同作用, 光催化制氢

Abstract:

Highly efficient TiO₂ photocatalysts (TiO₂/Ag-Ag₂O) co-modified by Ag as electron cocatalysts and Ag₂O as interfacial catalytic active sites were synthesized via a two-step process including the initial photoinduced deposition of metallic Ag nanoparticles on the TiO₂ surface (TiO₂/Ag) and the following in situ oxidation of partial Ag into Ag₂O by low-temperature calcination. Ag nanoparticles function as effective electron cocatalysts for the steady capture and rapid transportation of photogenerated electrons from TiO₂ surface to Ag₂O, while the adsorbed H⁺ ions from solution to Ag₂O as the interfacial catalytic active sites are reduced into H₂. The synergistic effect of Ag and Ag₂O can accelerate the electrons transfer and promote the rapid H₂-evolution reaction for enhanced photocatalytic H₂-evolution performance of TiO₂/Ag-Ag₂O. The highest H₂-evolution rate of the resultant TiO₂/Ag-Ag₂O calcinated at 300 ℃ reached 75.20 μmol/h, which was higher than those of the TiO₂ (3.59 μmol/h) and TiO₂/Ag (41.13 μmol/h) by 21.0 and 1.8 times, respectively. This study provides a new strategy for the design and synthesis of highly efficient photocatalytic H₂-evolution materials.

Key words: TiO₂, electron cocatalyst, interfacial catalytic active site, synergistic effect, photocatalytic H₂ evolution

中图分类号:

O643

王苹,李心宇,时占领,李海涛. Ag与Ag₂O协同增强TiO₂光催化制氢性能的研究[J]. 无机材料学报, 2020, 35(7): 781-788.

WANG Ping,LI Xinyu,SHI Zhanling,LI Haitao. Synergistic Effect of Ag and Ag₂O on Photocatalytic H₂-evolution Performance of TiO₂[J]. Journal of Inorganic Materials, 2020, 35(7): 781-788.

图/表 10

图1 (A) TiO2/Ag-Ag2O合成示意图和(B)对应样品照片

Fig. 1 (A) Schematic diagram of preparation for TiO2/Ag-Ag2O and (B) their corresponding photographs (a) TiO2-C; (b) TiO2/Ag; (c) TiO2/Ag-Ag2O(200); (d) TiO2/Ag-Ag2O (300); (e) TiO2/Ag-Ag2O(400)

图2 TiO2-C、TiO2/Ag和TiO2/Ag-Ag2O(x)的(A) XRD图谱、(B) 金属Ag的慢扫图谱和(C) Ag2O的慢扫图谱

Fig. 2 (A) XRD patterns, (B) diffraction peaks of metallic Ag and (C) diffraction peaks of Ag2O for TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)

图3 (A~F) TiO2-C、TiO2/Ag和TiO2/Ag-Ag2O(x)的FESEM照片(插图: EDX谱图和数据)和(G, H) TiO2/Ag-Ag2O(300) 的TEM照片

Fig. 3 (A-F) FESEM images of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)with insets showing their corresponding EDS spectra and data, and TEM images of TiO2/Ag-Ag2O(300) at low (G) and high (H) magnifications

图4 TiO2-C、TiO2/Ag和TiO2/Ag-Ag2O(x)的(A)XPS全谱和(B)Ag3d谱的高分辨率XPS谱; TiO2/Ag-Ag2O(300)样品的(C)Ag3d和(D)O1s典型峰的拟合曲线

Fig. 4 (A) XPS survey spectra and (B) the high-resolution XPS spectra of Ag3d spectra of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x), and typical fitting curves of (C)Ag3d and (D)O1s for TiO2/Ag-Ag2O(300)

表1 不同样品XPS的元素含量

Table 1 Contents of elements in various samples according to XPS analysis

Element	TiO₂-C	TiO₂/Ag	TiO₂/Ag-Ag₂O(200)	TiO₂/Ag-Ag₂O(300)	TiO₂/Ag-Ag₂O(400)
C1s/%	38.97	25.82	46.37	37.05	28.11
Ti2p/%	19.53	25.01	15.18	19.39	22.73
O1s/%	41.50	48.82	38.05	42.43	46.46
Ag3d/%	-	0.36	0.40	1.13	2.70
Ag⁺/Ag⁰	-	1.02	2.15	4.42	3.52

图5 TiO2-C、TiO2/Ag和TiO2/Ag-Ag2O(x)的UV-Vis吸收光谱及对应样品照片

Fig. 5 UV-Vis absorption spectra of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x) and their corresponding photographs (inset) (a) TiO2-C; (b) TiO2/Ag; (c) TiO2/Ag-Ag2O(200); (d) TiO2/Ag-Ag2O(300); (e) TiO2/Ag-Ag2O(400)

图6 (A) TiO2-C、TiO2/Ag和TiO2/Ag-Ag2O(x)的光催化制氢性能; (B) TiO2/Ag-Ag2O(300)的循环性能

Fig. 6 (A) Photocatalytic H2-evolution activity of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x), and (B) cycling performance of TiO2/Ag-Ag2O(300)

图7 TiO2/Ag-Ag2O的光催化制氢机理示意图

Fig. 7 Schematic diagram of photocatalytic H2-evolution mechanism of TiO2/Ag-Ag2O

图8 TiO2-C、TiO2/Ag和TiO2/Ag-Ag2O(x)的(A)线性扫描曲线(LSV)、(B)瞬态光电流响应和(C)电化学阻抗谱(EIS)

Fig. 8 (A) Linear sweep voltammetry (LSV) curves, (B) transient photocurrent responses, and (C) electrochemical impedance spectra (EIS) of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)

图9 TiO2-C、TiO2/Ag和TiO2/Ag-Ag2O(x)的荧光光谱图

Fig. 9 Photoluminescence (PL) spectra of TiO2-C, TiO2/Ag and TiO2/Ag-Ag2O(x)

参考文献 26

[1]	DU H, LIU Y, SHENG C, et al. Nanoheterostructured photocatalysts for improving photocatalytic hydrogen production. Chinese Journal of Catalysis, 2017,38(8):1295-1306. DOI URL
[2]	ZHANG K, PARK J H. Surface localization of defects in black TiO₂: enhancing photoactivity or reactivity. Journal of Physical Chemistry C, 2017,8:199-207.
[3]	LIU Q, SHEN J, YU X, et al. Unveiling the origin of boosted photocatalytic hydrogen evolution in simultaneously (S, P, O)- codoped and exfoliated ultrathin g-C₃N₄ nanosheets. Applied Catalysis B: Environmental, 2019,248:84-94. DOI URL
[4]	TIAN L, YANG X, LIU Q, et al. Anchoring metal-organic framework nanoparticles on graphitic carbon nitrides for solar-driven photocatalytic hydrogen evolution. Applied Surface Science, 2018,455:403-409. DOI URL
[5]	MA Y, LI Q. Preparation and characterization of TiO₂/Co₃O₄ nanocomposites and their photocatalytic activity for hydrogen evolution. Journal of Inorganic Materials, 2016,31(8):841-844. DOI URL
[6]	JIANG Y, QUA F, TIAN L, et al. Self-assembled g-C₃N₄ nanoarchitectures with boosted photocatalytic solar-to-hydrogen efficiency. Applied Surface Science, 2019,487:59-67. DOI URL
[7]	WEI J, LI X, WANG H, et al. Nitrogen doped carbon quantum dots/titanium dioxide composites for hydrogen evolution under sunlight. Journal of Inorganic Materials, 2015,30(9):925-930. DOI URL
[8]	YAN C, XUE X, ZHANG W, et al. Well-designed Te/SnS₂/Ag artificial nanoleaves for enabling and enhancing visible-light driven overall splitting of pure water. Nano Energy, 2017,39:539-545. DOI URL
[9]	LIU W, SHEN J, LIU Q, et al. Porous MoP network structure as co-catalyst for H₂ evolution over g-C₃N₄ nanosheets. Applied Surface Science, 2018,462:822-830. DOI URL
[10]	TANG H, WANG R, ZHAO C, et al. Oxamide-modified g-C₃N₄ nanostructures: tailoring surface topography for high-performance visible light photocatalysis. Chemical Engineering Journal, 2019,374:1064-1075. DOI URL
[11]	LI C, JIN H, YANG Z, et al. Preparation and photocatalytic properties of mesoporous RGO/TiO₂ composites. Journal of Inorganic Materials, 2017,32(04):357-364. DOI URL
[12]	WANG P, LU Y, WANG X, et al. Co-modification of amorphous-Ti(IV) hole cocatalyst and Ni(OH)₂ electron cocatalyst for enhanced photocatalytic H₂-production performance of TiO₂. Applied Surface Science, 2017,391:259-266. DOI URL
[13]	ZHANG W, ZHANG H, XU J, et al. 3D flower-like heterostructured TiO₂@Ni(OH)₂ microspheres for solar photocatalytic hydrogen production. Chinese Journal of Catalysis, 2019,40(3):320-325. DOI URL
[14]	KUMARAVEL V, MATHEW S, BARTIETT J, et al. Photocatalytic hydrogen production using metal doped TiO₂: a review of recent advances. Applied Catalysis B: Environmental, 2019,244:1021-1064. DOI URL
[15]	ZHAO D, YANG C F. Recent advances in the TiO₂/CdS nanocomposite used for photocatalytic hydrogen production and quantum-dot-sensitized solar cells. Renewable and Sustainable Energy Reviews, 2016,54:1048-1059. DOI URL
[16]	CHEN F, LUO W, Mo Y, et al. In situ photodeposition of amorphous CoS_x on the TiO₂ towards hydrogen evolution. Applied Surface Science, 2018,430:448-456. DOI URL
[17]	GUPTA B, MELVIN A A, MATTHEWS T, et al. TiO₂ modification by gold (Au) for photocatalytic hydrogen (H₂) production. Renewable and Sustainable Energy Reviews, 2016,58:1366-1375. DOI URL
[18]	HOU L, ZHANG M, GUAN Z, et al. Effect of platinum dispersion on photocatalytic performance of Pt-TiO₂. Journal of Nanoparticle Research, 2018,20(3):1-8. DOI URL
[19]	SARAVANAN R, MANOJ D, QIN J, et al. Mechanothermal synthesis of Ag/TiO₂ for photocatalytic methyl orange degradation and hydrogen production. Process Safety and Environmental Protection, 2018,120:339-347. DOI URL
[20]	WANG P, SHENG Y, WANG F, et al. Synergistic effect of electron-transfer mediator and interfacial catalytic active-site for the enhanced H₂ evolution performance: a case study of CdS/Au photocatalyst. Applied Catalysis B: Environmentai, 2018, 220:561-569.
[21]	YU H, LIU W, WANG X, et al. Promoting the interfacial H₂-evolution reaction of metallic Ag by Ag₂S cocatalyst: a case study of TiO₂/Ag-Ag₂S photocatalyst. Applied Catalysis B: Environmental, 2018, 225:415-423. DOI URL
[22]	WANG X, LIAO D, YU H, et al. Highly efficient BiVO₄ single-crystal photocatalyst with selective Ag₂O-Ag modification: orientation transport, rapid interfacial transfer and catalytic reaction. Dalton Transactions, 2018,47(18):6370-6377. DOI URL PMID
[23]	YU H, LIU R, WANG X, et al. Enhanced visible-light photocatalytic activity of Bi₂WO₆ nanoparticles by Ag₂O cocatalyst. Applied Catalysis B: Environmental, 2012, 111-112:326-333. DOI URL
[24]	LI J, HAO H, ZHOU J, et al. Ag@AgCl QDs decorated g-C₃N₄ nanoplates: the photoinduced charge transfer behavior under visible light and full arc irradiation. Applied Surface Science, 2017,422:626-637. DOI URL
[25]	KIM J, JUN H, HONG S, et al. Charge transfer in iron photoanode modified with carbon nanotubes for photoelectrochemical water oxidation: an electrochemical impendence study. International Journal of Hydrogen Energy, 2011,36:9462-9468. DOI URL
[26]	LIU Y, DING S, SHI Y, et al. Construction of CdS/CoO_x core-shell nanorods for efficient photocatalytic H₂ evolution. Applied Catalysis B: Environmental, 2018,234:106-116.

Ag与Ag₂O协同增强TiO₂光催化制氢性能的研究

Synergistic Effect of Ag and Ag₂O on Photocatalytic H₂-evolution Performance of TiO₂

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