Ti3C2 MXene纳米片上原位生长的Cd0.5Zn0.5S纳米棒实现高效可见光催化析氢

doi:10.3866/PKU.WHXB202402016

物理化学学报 >> 2025, Vol. 41 >> Issue (4): 100031.doi: 10.3866/PKU.WHXB202402016

Ti₃C₂ MXene纳米片上原位生长的Cd_0.5Zn_0.5S纳米棒实现高效可见光催化析氢

李钦¹, 张慧慧¹, 顾华军¹, 崔园园³, 高瑞华²^,*, 戴维林¹^,*()

¹ 复旦大学化学系, 上海市分子催化与创新材料重点实验室, 上海 200433
² 复旦大学高分子科学系, 聚合物分子工程国家重点实验室, 上海 200433
³ 岛津中国有限公司, 上海 200436

收稿日期:2024-02-19 修回日期:2024-04-03 录用日期:2024-04-03 发布日期:2024-12-28
通讯作者: Email: ruihuagao@fudan.edu.cn (高瑞华)wldai@fudan.edu.cn (戴维林)
基金资助:
科技部国家重点研发计划(2021YFA1501404); 上海市自然科学基金(22ZR1404200); 国家自然科学基金(21373054); 上海市科学技术委员会专项经费(19DZ2270100)

In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution

Qin Li¹, Huihui Zhang¹, Huajun Gu¹, Yuanyuan Cui³, Ruihua Gao²^,*, Wei-Lin Dai¹^,*()

¹ Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China
² State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, China
³ Shimadzu China Co LTD, Shanghai 200436, China

Received:2024-02-19 Revised:2024-04-03 Accepted:2024-04-03 Published:2024-12-28
Contact: Email: ruihuagao@fudan.edu.cn (Ruihua Gao)wldai@fudan.edu.cn (Wei-Lin Dai)
Supported by:
the National Key Research and Development Program of China(2021YFA1501404); Natural Science Foundation of Shanghai(22ZR1404200); National Natural Science Foundation of China(21373054); Natural Science Foundation of Shanghai Science and Technology Committee(19DZ2270100)

1. WHXB202402016-SI-6p.pdf(1123KB)

摘要/Abstract

摘要：

在能源短缺和环保优先的背景下，光催化制氢是将太阳能转化为化学能的重要途径之一。有效提高光生载流子的分离效率对于设计具有优异析氢活性的光催化剂至关重要。本研究采用一步原位水热法构建了由Cd_0.5Zn_0.5S纳米棒和Ti₃C₂ MXene纳米片组成的二元异质结光催化剂。当Ti₃C₂ MXene的含量为0.5 wt% (质量分数)时，光催化产氢的最大速率为15.56 mmol∙g⁻¹∙h⁻¹，是纯Cd_0.5Zn_0.5S的2.56倍。经过5次催化循环后，光催化活性没有显著下降。该材料在350 nm紫外光下展现出最高的AQE为18.4%。此外，基于X射线光电子能谱(XPS)、原位光照XPS、飞秒瞬态吸收光谱、密度泛函理论(DFT)计算和光催化活性实验，我们提出了MXene/Cd_0.5Zn_0.5S复合材料的电荷转移和光催化制氢机理。我们的研究表明，引入不含贵金属的MXene材料可以有效地帮助光生电子的转移。这项工作展示了MXene材料在构建高效低成本的制氢光催化剂方面的潜力。

关键词: Cd_1-xZn_xS纳米棒, 光催化, 析氢, Ti₃C₂-MXene纳米片, 异质结

Abstract:

Against the backdrop of energy scarcities and ecological concerns, the process of photocatalytic hydrogen evolution emerges as a critical method for transforming solar energy into chemical energy. Central to this technology is the crafting of photocatalysts that are not only efficient and durable but also economically viable. The key to creating photocatalysts that boast superior hydrogen production capabilities lies in enhancing the separation and transfer of photo-generated electrons and holes. This study introduces a binary heterojunction photocatalyst, featuring a combination of Cd_0.5Zn_0.5S and Ti₃C₂ MXene, synthesized via an in situ hydrothermal method. In the composite, slender Cd_0.5Zn_0.5S nanorods are uniformly coated over the surface of single layer Ti₃C₂ nanosheets, forming a Schottky heterojunction at the material interface. This structure enhances the separation efficiency of photo-generated electrons and holes, thereby improving the utilization of light. With 0.5 wt% (mass fraction) of Ti₃C₂ MXene incorporated, we observed a peak photocatalytic H₂ generation rate of 15.56 mmol∙g⁻¹∙h⁻¹, outperforming the baseline Cd_0.5Zn_0.5S by 2.56 times. Notably, the photocatalytic efficiency remained largely unchanged after five cycles. This composite achieved the highest apparent quantum efficiency (AQE) of 18.4% when exposed to 350 nm UV light. Various characterization techniques, including in situ X-ray photoelectron spectroscopy (XPS) and femtosecond transient absorption (fs-TA) spectroscopy, along with density functional theory (DFT) calculations, have further substantiated that the formation of a Schottky heterojunction at the interface is crucial for enhancing the photocatalytic hydrogen evolution performance of the composite material. This paper demonstrates the effectiveness of the novel carbon based material MXene as a co-catalyst for improving the performance of photocatalysts and offers a viable approach for the construction of MXene-containing photocatalytic hydrogen evolution catalysts.

Key words: Cd_1-xZn_xS nanorods, Photocatalysis, Hydrogen evolution, Ti₃C₂ MXene nanosheet, Heterojunction

李钦, 张慧慧, 顾华军, 崔园园, 高瑞华, 戴维林. Ti₃C₂ MXene纳米片上原位生长的Cd_0.5Zn_0.5S纳米棒实现高效可见光催化析氢[J]. 物理化学学报, 2025, 41(4), 100031. doi: 10.3866/PKU.WHXB202402016

Qin Li, Huihui Zhang, Huajun Gu, Yuanyuan Cui, Ruihua Gao, Wei-Lin Dai. In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution[J]. Acta Phys. -Chim. Sin. 2025, 41(4), 100031. doi: 10.3866/PKU.WHXB202402016

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202402016

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I4/100031

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参考文献 59

1	Wang Z. ; Li C. ; Domen K. Chem. Soc. Rev. 2019, 48 (7), 2109. doi: 10.1039/C8CS00542G
2	Chen X. ; Shen S. ; Guo L. ; Mao S. S. Chem. Rev. 2010, 110 (11), 6503. doi: 10.1021/cr1001645
3	Fujishima A. ; Honda K. Nature 1972, 238 (5358), 37. doi: 10.1038/238037a0
4	Wang X. ; Maeda K. ; Thomas A. ; Takanabe K. ; Xin G. ; Carlsson J. M. ; Domen K. ; Antonietti M. Nat. Mater. 2009, 8, 76. doi: 10.1038/nmat2317
5	Liu J. ; Liu Y. ; Liu N. ; Han Y. ; Zhang X. ; Huang H. ; Lifshitz Y. ; Lee S.-T. ; Zhong J. ; Kang Z. Science 2015, 347 (6225), 970. doi: 10.1126/science.aaa3145
6	Song Y. ; Li Z. ; Zhu Y. ; Feng X. ; Chen J. S. ; Kaufmann M. ; Wang C. ; Lin W. J. Am. Chem. Soc. 2019, 141 (31), 12219. doi: 10.1021/jacs.9b05964
7	Kumar D.P. ; Hong S. ; Reddy D. A. ; Kim T. K. Appl. Catal. B-Environ. 2017, 212, 7. doi: 10.1016/j.apcatb.2017.04.065
8	Zhang Q. ; Wang X. ; Zhang J. ; Li L. ; Gu H. ; Dai W.-L. J. Colloid Interface Sci. 2021, 590, 632. doi: 10.1016/j.jcis.2021.01.083
9	Zhang L. ; Ding N. ; Lou L. ; Iwasaki K. ; Wu H. ; Luo Y. ; Li D. ; Nakata K. ; Fujishima A. ; Meng Q. Adv. Funct. Mater. 2019, 29 (3), 1806774. doi: 10.1002/adfm.201806774
10	Zhang L. ; Cui Y. ; Yang F. ; Zhang Q. ; Zhang J. ; Cao M. ; Dai W.-L. J. Mater. Sci. Technol. 2020, 45, 176. doi: 10.1016/j.jmst.2019.11.020
11	Wang J. ; Shen Y. ; Liu S. ; Zhang Y. Appl. Catal. B-Environ. 2020, 270, 118885. doi: 10.1016/j.apcatb.2020.118885
12	Shehzad N. ; Tahir M. ; Johari K. ; Murugesan T. ; Hussain M. Appl. Surf. Sci. 2019, 463, 445. doi: 10.1016/j.apsusc.2018.08.250
13	Cadiau A. ; Kolobov N. ; Srinivasan S. ; Goesten M. G. ; Haspel H. ; Bavykina A. V. ; Tchalala M. R. ; Maity P. ; Goryachev A. ; Poryvaev A. S. ; et al Angew. Chem.-Int. Ed. 2020, 59 (32), 13468. doi: 10.1002/anie.202000158
14	Zhu Y.-P. ; Yin J. ; Abou-Hamad E. ; Liu X. ; Chen W. ; Yao T. ; Mohammed O. F. ; Alshareef H. N. Adv. Mater. 2020, 32 (16), 1906368. doi: 10.1002/adma.v32.1610.1002/adma.201906368
15	Zhou P. ; Zhang Q. ; Xu Z. ; Shang Q. ; Wang L. ; Chao Y. ; Li Y. ; Chen H. ; Lv F. ; Zhang Q. ; et al Adv. Mater. 2020, 32 (7), 1904249. doi: 10.1002/adma.201904249
16	Ruan D. ; Fujitsuka M. ; Majima T. Appl. Catal. B-Environ. 2020, 264, 118541. doi: 10.1016/j.apcatb.2019.118541
17	Tian L. ; Min S. ; Wang F. Appl. Catal. B-Environ. 2019, 259, 118029. doi: 10.1016/j.apcatb.2019.118029
18	Yue X. ; Yi S. ; Wang R. ; Zhang Z. ; Qiu S. Appl. Catal. B-Environ. 2018, 224, 17. doi: 10.1016/j.apcatb.2017.10.010
19	Luo Z. ; Zhao X. ; Zhang H. ; Jiang Y. Appl. Catal. A-Gen. 2019, 582, 117115. doi: 10.1016/j.apcata.2019.117115
20	Huang H.-B. ; Fang Z.-B. ; Yu K. ; Lü J. ; Cao R. J. Mater. Chem. A 2020, 8 (7), 3882. doi: 10.1039/C9TA13836F
21	Li Q. ; Meng H. ; Zhou P. ; Zheng Y. ; Wang J. ; Yu J. ; Gong J. Gong, J. ACS Catal. 2013, 3 (5), 882. doi: 10.1021/cs4000975
22	Hou Y. ; Laursen A. B. ; Zhang J. ; Zhang G. ; Zhu Y. ; Wang X. ; Dahl S. ; Chorkendorff I. Angew. Chem.-Int. Ed. 2013, 52 (13), 3621. doi: 10.1002/anie.201210294
23	Naguib M. ; Kurtoglu M. ; Presser V. ; Lu J. ; Niu J. ; Min H. ; Hultman L. ; Gogotsi Y. ; Barsoum M. W. Adv. Mater. 2011, 23 (37), 4248. doi: 10.1002/adma.201102306
24	Zhang Q. ; Lai H. ; Fan R. ; Ji P. ; Fu X. ; Li H. ACS Nano 2021, 15 (3), 5249. doi: 10.1021/acsnano.0c10671
25	Zhang Q. ; Fan R. ; Cheng W. ; Ji P. ; Sheng J. ; Liao Q. ; Lai H. ; Fu X. ; Zhang C. ; Li H. Adv. Sci. 2022, 9 (28), 2202748. doi: 10.1002/advs.202202748
26	Zhang Q. ; Zhang Z. ; Zhao D. ; Wang L. ; Li H. ; Zhang F. ; Huo Y. ; Li H. Appl. Catal. B-Environ. 2023, 320, 122009. doi: 10.1016/j.apcatb.2022.122009
27	Tang X. ; Zhou D. ; Li P. ; Guo X. ; Sun B. ; Liu H. ; Yan K. ; Gogotsi Y. ; Wang G. Adv. Mater. 2020, 32 (4), 1906739. doi: 10.1002/adma.201906739
28	Zhang Q. ; He J. ; Fu X. ; Xie S. ; Fan R. ; Lai H. ; Cheng W. ; Ji P. ; Sheng J. ; Liao Q. ; Zhu W. ; Li H. Chem. Eng. J. 2022, 430, 132950. doi: 10.1016/j.cej.2021.132950
29	Zhou Y. ; Maleski K. ; Anasori B. ; Thostenson J.O. ; Pang Y. ; Feng Y. ; Zeng K. ; Parker C. B. ; Zauscher S. ; Gogotsi Y. ; Glass J. T. ; Cao C. ACS Nano 2020, 14 (3), 3576. doi: 10.1021/acsnano.9b10066
30	Li Y. ; Yin Z. ; Ji G. ; Liang Z. ; Xue Y. ; Guo Y. ; Tian J. ; Wang X. ; Cui H. Appl. Catal. B-Environ. 2019, 246, 12. doi: 10.1016/j.apcatb.2019.01.051
31	Wu Y. ; Li X. ; Yang Q. ; Wang D. ; Yao F. ; Cao J. ; Chen Z. ; Huang X. ; Yang Y. ; Li X. Chem. Eng. J. 2020, 390, 124519. doi: 10.1016/j.cej.2020.124519
32	Cheng L. ; Chen Q. ; Li J. ; Liu H. Appl. Catal. B-Environ. 2020, 267, 118379. doi: 10.1016/j.apcatb.2019.118379
33	Shao M. ; Shao Y. ; Chai J. ; Qu Y. ; Yang M. ; Wang Z. ; Yang M. ; Ip W. F. ; Kwok C. T. ; Shi X. ; et al J. Mater. Chem. A 2017, 5, 16748. doi: 10.1039/C7TA04122E
34	Kwon N. H. ; Shin S.-J. ; Jin X. ; Jung Y. ; Hwang G.-S. ; Kim H. ; Hwang S.-J. Appl. Catal. B-Environ. 2020, 277, 19191. doi: 10.1016/j.apcatb.2020.119191
35	Huang Y. ; Mei F. ; Zhang J. ; Dai K. ; Dawson G. Acta Phys.-Chim. Sin. 2022, 38 (7), 2108028. doi: 10.3866/PKU.WHXB202108028
36	Yang H. ; Dai K. ; Zhang J. ; Dawson G. Chin. J. Catal. 2022, 43 (8), 2111. doi: 10.1016/S1872-2067(22)64096-8
37	Wang Z. ; Wang J. ; Zhang J. ; Dai K. Acta Phys. -Chim. Sin. 2023, 39 (6), 2209037. doi: 10.3866/PKU.WHXB202209037
38	Hua J. ; Wang Z. ; Zhang J. ; Dai K. ; Shao C. ; Fan K. J. Mater. Sci. Technol. 2023, 156, 64. doi: 10.1016/j.jmst.2023.03.003
39	Zhao Z. ; Wang Z. ; Zhang J. ; Shao C. ; Dai K. ; Fan K. ; Liang C. Adv. Funct. Mater. 2023, 33, 2214470. doi: 10.1002/adfm.202214470
40	Zhang H. ; Wang Z. ; Zhang J. ; Dai K. Chin. J. Catal. 2023, 49, 42. doi: 10.1016/S1872-2067(23)64444-4
41	Li Y.-H. ; Zhang F. ; Chen Y. ; Li J.-Y. ; Xu Y.-J. Green. Chem. 2020, 22, 163. doi: 10.1039/c9gc03332g
42	Li Z. ; Huang W. ; Liu J. ; Lv K. ; Li Q. ACS Catal. 2021, 11 (14), 8510. doi: 10.1021/acscatal.1c02018
43	Gu H. ; Zhang H. ; Wang X. ; Li Q. ; Chang S. ; Huang Y. ; Gao L. ; Cui Y. ; Liu R. ; Dai W.-L. Appl. Catal. B-Environ. 2023, 328, 122537. doi: 10.1016/j.apcatb.2023.122537
44	Sun B. ; Qiu P. ; Liang Z. ; Xue Y. ; Zhang X. ; Yang L. ; Cui H. ; Tian J. Chem. Eng. J. 2021, 406, 127177. doi: 10.1016/j.cej.2020.127177
45	Xiao R. ; Zhao C. ; Zou Z. ; Chen Z. ; Tian L. ; Xu H. ; Tang H. ; Liu Q. ; Lin Z. ; Yang X. Appl. Catal. B-Environ. 2020, 268, 118382. doi: 10.1016/j.apcatb.2019.118382
46	Saini B. ; Laishram H. K. D. ; Krishnapriya R. ; Singhal R. ; Sharma R. K. ACS Appl. Nano Mater. 2022, 5 (7), 9319. doi: 10.1021/acsanm.2c01639
47	Zhu S.-C. ; Li S. ; Tang B. ; Liang H. ; Liu B.-J. ; Xiao G. ; Xiao F.-X. J. Catal. 2021, 404, 56. doi: 10.1016/j.jcat.2021.09.001
48	Zhu S.-C. ; Wang Z.-C. ; Tang B. ; Liang H. ; Liu B.-J. ; Li S. ; Chen Z. ; Cheng N. C. ; Xiao F.-X. J. Mater. Chem. A 2022, 10, 11926. doi: 10.1039/D2TA02755K
49	He F. ; Zhu B. ; Cheng B. ; Yu J. ; Ho W. ; Macyk W. Appl. Catal. B- Environ. 2020, 272, 119006. doi: 10.1016/j.apcatb.2020.119006
50	Huang W. ; Li Z. ; Wu C. ; Zhang H. ; Sun J. ; Li Q. J. Mater. Sci. Technol. 2022, 120, 89. doi: 10.1016/j.jmst.2021.12.028
51	Huang W.-X. ; Li Z.-P. ; Li D.-D. ; Hu Z.-H. ; Wu C. ; Lv K.-L. ; Li Q. Rare Met. 2022, 41, 3268. doi: 10.1007/s12598-022-02058-2
52	Li H. ; Sun B. ; Gao T. ; Li H. ; Ren Y. ; Zhou G. Chin. J. Catal. 2022, 43 (2), 461. doi: 10.1016/S1872-2067(21)63915-3
53	Guan C. ; Yue X. ; Fan J. ; Xiang Q. Chin. J. Catal. 2022, 43 (10), 2484. doi: 10.1016/S1872-2067(22)64102-0
54	You Z. ; Liao Y. ; Li X. ; Fan J. ; Xiang Q. Nanoscale 2021, 13, 9463. doi: 10.1039/D1NR02224E
55	Su T. ; Men C. ; Chen L. ; Chu B. ; Luo X. ; Ji H. ; Chen J. ; Qin Z. Adv. Sci. 2022, 9, 2103715. doi: 10.1002/advs.202103715
56	Yu J. ; Zhang J. ; Jaroniec M. Green Chem. 2010, 12, 1611. doi: 10.1039/c0gc00236d
57	Sun Q.-M. ; Xu J.-J. ; Tao F.-F. ; Ye W. ; Zhou C. ; He J.-H. ; Lu J.-M. Angew. Chem.-Int. Ed. 2022, 61, e202200872. doi: 10.1002/anie.202200872
58	Zhu J. ; Wageh S. ; Al-Ghamdi A. A. Chin. J. Catal. 2023, 49, 5. doi: 10.1016/S1872-2067(23)64438-9
59	Cheng C. ; Zhang J. ; Zhu B. ; Liang G. ; Zhang L. ; Yu J. Angew. Chem.-Int. Ed. 2023, 62, e202218688. doi: 10.1002/anie.202218688

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Ti₃C₂ MXene纳米片上原位生长的Cd_0.5Zn_0.5S纳米棒实现高效可见光催化析氢

In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution

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