光沉积Pt复合石墨相氮化碳实现高效光催化产氢

牛凤延; 何齐升; 武世然; 郭晨曦; 雷伟岩; 沈毅

doi:10.13801/j.cnki.fhclxb.20230614.001

光沉积Pt复合石墨相氮化碳实现高效光催化产氢

doi: 10.13801/j.cnki.fhclxb.20230614.001

1.
华北理工大学　材料科学与工程学院，唐山 063210
2.
华北理工大学　矿业与工程学院，唐山 063210

基金项目: 国家自然科学基金 (51772099；51572069)

详细信息

通讯作者:
沈毅，博士，教授，博士生导师，研究方向为光催化材料　E-mail: shenyinfy@163.com

中图分类号: TB333
计量
- 文章访问数: 592
- HTML全文浏览量: 294
- PDF下载量: 40
- 被引次数: 0
出版历程
- 收稿日期: 2023-04-11
- 修回日期: 2023-05-18
- 录用日期: 2023-05-26
- 网络出版日期: 2023-06-14
- 刊出日期: 2024-01-01

Photodeposition Pt composite graphitic carbon nitride realizes efficient photocatalytic hydrogen production

1.
College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, China
2.
College of Mining Engineering, North China University of Science and Technology, Tangshan 063210, China

Funds: National Natural Science Foundation of China (51772099; 51572069)

摘要

摘要: 贵金属作为助催化剂，可以提高石墨相氮化碳(g-C₃N₄)光催化产氢的性能，引起了人们的广泛关注。但是，由于贵金属的不可再生性和高价格，“更少的贵金属，更好的性能”始终是目标。为了实现这一目标，通过光沉积还原法成功制备了一系列不同铂负载量氮化碳复合材料(Pt/CN)，并用于光催化产H₂。结果表明：不同Pt负载量的Pt/CN复合材料都表现出优异的光催化产氢性能。并发现当Pt的负载量为0.5wt%时， Pt/CN复合材料具有最优异的光催化产氢活性，产氢量为409.2 μmol/g，是纯CN (17.8 μmol/g)的23倍，同时证实了Pt和CN二者之间形成了肖特基势垒，使导带的电子快速迁移到Pt上，降低了CN的电子-空穴复合速率。并且Pt作为光催化分解水的活性位点，促进水中的绝大部分氢质子快速吸附到Pt位点，得到电子被还原为H₂，实现了高效光催化产氢。
- 石墨相氮化碳 /
- 光催化产氢 /
- 铂 /
- 光沉积 /
- 复合比
Abstract: Noble-metal, as co-catalysts, can improve the photocatalytic hydrogen production performance of graphitic carbon nitride (g-C₃N₄). It has been paid extensive attention, however, due to the non-renewability and high expense of noble-metal, "less noble-metal, better performance" is always the goal. To achieve this goal, composite CN with different Pt loadings (Pt/CN) was successfully prepared by photoreduction deposition and used for photocatalytic hydrogen production. The results show that Pt/CN with different Pt loadings can improved photocatalytic hydrogen production performance than CN. It is found that Pt/CN loaded with 0.5wt%Pt have the best photocatalytic hydrogen production activity, with a hydrogen production rate of 409.2 μmol/g, which is 23 times higher than that of CN (17.8 μmol/g). At the same time, it is confirmed that a Schottky barrier is formed between Pt and CN, which makes the electrons of the conduction band migrate rapidly to Pt, which reduces the electron-hole recombination rate of CN. Moreover, Pt is used as the active site of photocatalytic water splitting, which promotes the rapid adsorption of most of the hydrogen protons in the water to the Pt site, and the electrons are reduced to hydrogen, realizing efficient photocatalytic hydrogen production.
- graphitic carbon nitride /
- photocatalytic hydrogen production /
- Pt /
- photodeposition /
- compound rad

HTML全文

图 1 石墨相氮化碳(CN) (a) 和Pt/CN (b) 的制备

Figure 1. Synthesis of graphitic carbon nitride (CN) (a) and Pt/CN (b)

g-C₃N₄—Graphitic carbon nitride (CN)

下载: 全尺寸图片幻灯片

图 2 不同Pt负载量下Pt/CN的XRD图谱(a)和FTIR图谱(b)

Figure 2. XRD patterns (a) and FTIR spectra (b) of Pt/CN under different Pt doping amounts

下载: 全尺寸图片幻灯片

图 3 0.5wt%Pt/CN 样品的TEM图像((a), (b))、EDS能谱(插表为ZAF法无标定量分析) (c)、Mapping ((d)~(g))

Figure 3. TEM images ((a), (b)), EDS energy spectrum (Insert table is Zahl absorption fluorescence method (ZAF) standardless quantitative analysis) (c), mapping ((d)-(g)) of 0.5wt%Pt/CN sample

下载: 全尺寸图片幻灯片

图 4 CN (a)和0.5wt%Pt/CN复合材料(b)的氮气吸附-脱附曲线及孔径分布图(c)

Figure 4. Nitrogen adsorption-desorption curve of CN (a) and 0.5wt%Pt/CN composites (b) and pore size distribution (c)

STP—Standard temperature and pressure

下载: 全尺寸图片幻灯片

图 5 不同Pt负载量下Pt/CN的UV-vis DRS (a)、Tauc-plot图(b)、PL光谱(c)、EIS (d)、瞬时光响应电流图(e)

Figure 5. UV-vis DRS (a), Tauc-plot (b), PL spectra (c), EIS (d), transient photocurrent density (e) of Pt/CN under different Pt doping amounts

下载: 全尺寸图片幻灯片

图 6 (a)不同Pt负载量下Pt/CN的光解水产H₂曲线；(b) 0.5wt%Pt/CN的循环光催化测试；反应前后0.5wt%Pt/CN的XRD图谱(c)和FTIR图谱(d)

Figure 6. (a) Photolyzed aquatic H₂ curves of Pt/CN under different Pt doping amounts; (b) Cycling photocatalytic test of 0.5wt%Pt/CN; XRD patterns (c) and FTIR spectra (d) of 0.5wt%Pt/CN before and after reaction

下载: 全尺寸图片幻灯片

图 7 Pt/CN 复合光催化产氢过程

Figure 7. Pt/CN composite photocatalytic hydrogen production process

下载: 全尺寸图片幻灯片

参考文献(22)

[1]	KARTHIKEYAN C, ARUNACHALAM P, RAMACHANDRAN K, et al. Recent advances in semiconductor metal oxides with enhanced methods for solar photocatalytic applications[J]. Journal of Alloys and Compounds,2020,828:154281. doi: 10.1016/j.jallcom.2020.154281
[2]	ZHANG S, WANG K, LI F, et al. Structure-mechanism relationship for enhancing photocatalytic H₂ production[J]. International Journal of Hydrogen Energy,2022,47(88):37517-37530. doi: 10.1016/j.ijhydene.2021.10.139
[3]	XIONG S, TANG R, GONG D, et al. Environmentally-friendly carbon nanomaterials for photocatalytic hydrogen production[J]. Chinese Journal of Catalysis,2022,43(7):1719-1748. doi: 10.1016/S1872-2067(21)63994-3
[4]	MUN S J, PARK S J. Graphitic carbon nitride materials for photocatalytic hydrogen production via water splitting: A short review[J]. Catalysts,2019,9(10):805. doi: 10.3390/catal9100805
[5]	ZHOU Y Z, ZHANG L X, QIN L X, et al. A mixed phase lanthanum vanadate in situ induced by graphene oxide/graphite carbon nitride for efficient photocatalytic hydrogen generation[J]. International Journal of Hydrogen Energy,2021,46(54):27495-27505. doi: 10.1016/j.ijhydene.2021.05.213
[6]	XUE F, CHEN C, FU W L, et al. Interfacial and dimensional effects of Pd co-catalyst for efficient photocatalytic hydrogen generation[J]. The Journal of Physical Chemistry C,2018,122(44):25165-25173. doi: 10.1021/acs.jpcc.8b06943
[7]	LI K, LIN Y Z, WANG K, et al. Rational design of cocatalyst system for improving the photocatalytic hydrogen evolution activity of graphite carbon nitride[J]. Applied Catalysis B: Environmental,2020,268:118402. doi: 10.1016/j.apcatb.2019.118402
[8]	WU Q K, JEONG T, KIM S H, et al. Synthesis of large area graphitic carbon nitride nanosheet by chemical vapor deposition[J]. Journal of Alloys and Compounds,2022,900:163310. doi: 10.1016/j.jallcom.2021.163310
[9]	DING L, QI F, LI Y F, et al. In-situ formation of nanosized 1T-phase MoS₂ in B-doped carbon nitride for high efficient visible-light-driven H₂ production[J]. Journal of Colloid and Interface Science,2022,614:92-101. doi: 10.1016/j.jcis.2022.01.100
[10]	JIANG W S, ZHAO Y J, ZONG X P, et al. Photocatalyst for high-performance H₂ production: Ga-doped polymeric carbon nitride[J]. Angewandte Chemie International Edition,2021,60(11):6124-6129. doi: 10.1002/anie.202015779
[11]	LIU Y, GAO M Y, YANG W W, et al. Facile synthesis of monodisperse Pt nanoparticles on graphitic carbon Nitride for high-performance photocatalytic H₂ evolution[J]. ChemistrySelect,2022,7(9):e202103882.
[12]	PENG Y, LU B Z, CHEN L M, et al. Hydrogen evolution reaction catalyzed by ruthenium ion-complexed graphitic carbon nitride nanosheets[J]. Journal of Materials Chemistry A,2017,5(34):18261-18269. doi: 10.1039/C7TA03826G
[13]	WU J E, ZHANG Y Y, ZHANG B, et al. Zn-doped CoS₂ nanoarrays for an efficient oxygen evolution reaction: Understanding the doping effect for a precatalyst[J]. ACS Applied Materials & Interfaces,2022,14(12):14235-14242.
[14]	HUANG L, LIU X, WU H C, et al. Surface state modulation for size-controllable photodeposition of noble metal nanoparticles on semiconductors[J]. Journal of Materials Chemistry A,2020,8(40):21094-21102. doi: 10.1039/C9TA14181B
[15]	BAI L, LI Y J, ZHAO J, et al. Highly efficient utilization of precious metals for hydrogen evolution reaction with photo-assisted electro-deposited urchin-like Te nano- structure as a template[J]. ChemCatChem,2019,11(9):2283-2287. doi: 10.1002/cctc.201900125
[16]	WU H C, LIU Y D, CHEN G L, et al. Surface-confined photodeposition of noble metal nanoclusters on TiO₂ in a fluidized bed for the catalytic oxidation of formaldehyde[J]. ACS Applied Nano Materials,2022,5(9):13100-13111. doi: 10.1021/acsanm.2c02886
[17]	KARÁCSONVI É, BAIA L, DONBI A, et al. The photocatalytic activity of TiO₂/WO₃/noble metal (Au or Pt) nanoarchitecture obtained by selective photodeposition[J]. Catalysis Today,2013,208:19-27. doi: 10.1016/j.cattod.2012.09.038
[18]	LIU Y D, NASERI A, LI T, et al. Shape-controlled photochemical synthesis of noble metal nanocrystals based on reduced graphene oxide[J]. ACS Applied Materials & Interfaces,2022,14(14):16527-16537.
[19]	ONG W J, TAN L L, CHAI S P, et al. Heterojunction engineering of graphitic carbon nitride (g-C₃N₄) via Pt loading with improved daylight-induced photocatalytic reduction of carbon dioxide to methane[J]. Dalton Transactions,2015,44(3):1249-1257. doi: 10.1039/C4DT02940B
[20]	LIU Z, HUO P, LU Z, et al. Fabrication of magnetically recoverable photocatalysts using g-C₃N₄ for effective separation of charge carriers through like-Z-scheme mechanism with Fe₃O₄ mediator[J]. Chemical Engineering Journal,2018,331:615-625. doi: 10.1016/j.cej.2017.08.131
[21]	孟培媛, 郭明媛, 乔勋. WS₂/g-C₃N₄异质结光催化分解水制氢性能及机制[J]. 复合材料学报, 2021, 38(2):591-600. MENG Peiyuan, GUO Mingyuan, QIAO Xun. H₂ production performance of photocatalyst and mechanism of WS₂/g-C₃N₄ heterojunction[J]. Acta Materiae Compositae Sinica,2021,38(2):591-600(in Chinese).
[22]	孙术博, 于海瀚, 李强, 等. NaNbO₃@g-C₃N₄复合材料的可控构筑及其压电光催化性能[J]. 复合材料学报, 2023, 40(3):1534-1540. SUN Shubo, YU Haihan, LI Qiang, et al. Controlled construction of NaNbO₃@g-C₃N₄ composites and their piezo-photocatalytic properties[J]. Acta Materiae Compositae Sinica,2023,40(3):1534-1540(in Chinese).