金属-有机骨架衍生的Ni-CNT/ZnIn2S4异质结用于光催化产氢及其电荷转移途径的确定

doi:10.3866/PKU.WHXB202304018

物理化学学报 >> 2024, Vol. 40 >> Issue (1): 2304018.doi: 10.3866/PKU.WHXB202304018

论文上一篇

金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定

赖可溱¹^,², 李丰彦¹^,², 李宁¹^,², 高旸钦¹^,², 戈磊¹^,²^,*()

¹ 中国石油大学(北京)新能源与材料学院重质油国家重点实验室, 北京 102249
² 中国石油大学(北京)新能源与材料学院材料科学与工程系, 北京 102249

收稿日期:2023-04-06 修回日期:2023-05-20 录用日期:2023-05-22 发布日期:2023-08-21
通讯作者: Email: gelei@cup.edu.cn; Tel.: +86-18890325013 (戈磊)
基金资助:
国家重点研发计划(2021YFA1501300); 国家重点研发计划(2019YFC1907602); 国家自然科学基金(51572295); 国家自然科学基金(21273285); 国家自然科学基金(21003157)

Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution

Kezhen Lai¹^,², Fengyan Li¹^,², Ning Li¹^,², Yangqin Gao¹^,², Lei Ge¹^,²^,*()

¹ State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China
² Department of Materials Science and Engineering, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China

Received:2023-04-06 Revised:2023-05-20 Accepted:2023-05-22 Published:2023-08-21
Contact: Email: gelei@cup.edu.cn; Tel.: +86-18890325013 (Lei Ge)
Supported by:
the National Key R & D Program of China(2021YFA1501300); the National Key R & D Program of China(2019YFC1907602); National Natural Science Foundation of China(51572295); National Natural Science Foundation of China(21273285); National Natural Science Foundation of China(21003157)

摘要/Abstract

摘要：

氢气是缓解环境污染和能源短缺的零污染绿色能源，利用太阳能诱导半导体裂解水制氢是最环保的方法之一。本文以MOFs衍生的Ni-CNT(Ni修饰的碳纳米管)作为非贵金属助催化剂，通过简单的油浴法原位生长ZnIn₂S₄纳米片合成了Ni-CNT/ZnIn₂S₄。在Ni-CNT/ZnIn₂S₄中，Ni纳米颗粒包裹在CNT的顶部和横截面上，有效地阻止了Ni纳米颗粒的团聚。Ni-CNT/ZnIn₂S₄异质结构具有紧密的接触界面，有利于电荷转移，可作为高效的析氢光催化剂。38Ni-CNT/ZnIn₂S₄样品具有最佳的产氢性能(12267 μmol·h⁻¹·g⁻¹)，约为纯ZnIn₂S₄的6.4倍，且在420 nm单色光下其表观量子效率达到11.3%。X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)结果证实了Ni-CNT/ZnIn₂S₄异质结构的存在。电化学测试表明，Ni-CNT与ZnIn₂S₄的结合促进了光生电荷的转移，有效地阻止了光生载流子的快速复合，从而增强了ZnIn₂S₄的析氢性能。电子自旋共振(ESR)结果进一步证明了Ni-CNT助催化剂的存在延长了ZnIn₂S₄光生电荷的寿命，促进了光生电荷和空穴的分离效率。通过密度泛函理论计算探索并确定了异质结界面中的电荷转移途径。Ni、CNT和ZnIn₂S₄费米能级的差异导致界面处电荷发生迁移从而形成内嵌电场，ZnIn₂S₄的能带向下弯曲，促进光生电子从ZnIn₂S₄流向Ni-CNT电子受体。平面平均电子密度差结果证实了热电子从Ni转移至CNT再转移至ZnIn₂S₄，表明光生电子转移途径为ZnIn₂S₄ → CNT → Ni。此外，吸附H*吉布斯自由能(ΔG_H*)和晶体轨道哈密顿布居(COHP)结果表明Ni纳米颗粒可作为析氢反应的活性位点，促进了产氢效率。本工作将为开发低成本、高效的非贵金属光催化制氢催化剂提供新的策略。

关键词: Ni-CNT, 光催化, 析氢, ZnIn₂S₄, 助催化剂

Abstract:

Hydrogen is an important zero-pollution green energy source with potential for alleviating environmental contamination and energy shortages. Hydrogen evolution via solar-energy-induced semiconducting water splitting is among the most environmentally friendly methods available to date. In this study, a metal–organic-framework-derived, Ni-decorated carbon nanotube (Ni-CNT) is used as a non-noble co-catalyst. This Ni-CNT is grown in situ on ZnIn₂S₄ nanosheets using a simple one-step oil bath strategy, wherein Ni nanoparticles are wrapped around the top and cross sections of the nanotubes, preventing their agglomeration. Notably, Ni-CNT/ZnIn₂S₄ heterostructures feature intimate contact interfaces that promote charge transfer, facilitating their use as efficient photocatalysts for hydrogen evolution. The 38Ni-CNT/ZnIn₂S₄ sample exhibits a high H₂ production rate (12267 μmol·h⁻¹·g⁻¹), with an apparent quantum efficiency (AQE) of 11.3% under 420 nm monochromatic light irradiation, which is nearly 6.4 times that of pure ZnIn₂S₄. The results of X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) corroborate the observations on Ni-CNT/ZnIn₂S₄ heterostructures. Electrochemical measurements reveal that the combination of the Ni-CNT and ZnIn₂S₄ facilitates the transfer of photogenerated electrons and effectively prevents rapid recombination of photocarriers, thus improving the hydrogen evolution performance of ZnIn₂S₄. Electron spin resonance (ESR) results further prove that co-catalyst Ni-CNTs are beneficial for prolonging the lifetimes of ZnIn₂S₄ photogenerated electrons, thereby achieving effective charge separation. A charge transfer pathway in the heterojunction interfaces is further explored and confirmed by density functional theory (DFT) calculations. The difference in the Fermi level energy (E_f) contributes to both charge migration and the generation of a built-in electronic field (BEF), indicating that the energy band of ZnIn₂S₄ bends downward, which is favorable for photogenerated electron flow from ZnIn₂S₄ to the Ni-CNT electron acceptor. The results of planar-averaged electron density difference analysis confirm that the hot electrons are transferred from Ni nanoparticles to the CNT and then to the ZnIn₂S₄ nanosheets, indicating the formation of a photogenerated electron transfer pathway of ZnIn₂S₄ → CNT → Ni. Furthermore, Gibbs free energy of H* adsorption (ΔG_H*) and crystal orbital Hamilton population (COHP) analysis indicate that Ni nanoparticles can serve as active sites, promoting H₂ evolution. Thus, the present study formulates a new strategy for developing low-cost, high-efficiency, non-noble-metal co-catalysts for photocatalytic hydrogen production.

Key words: Ni-CNT, Photocatalysis, H₂ evolution, ZnIn₂S₄, Co-catalysts

赖可溱, 李丰彦, 李宁, 高旸钦, 戈磊. 金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定[J]. 物理化学学报, 2024, 40(1), 2304018. doi: 10.3866/PKU.WHXB202304018

Kezhen Lai, Fengyan Li, Ning Li, Yangqin Gao, Lei Ge. Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution[J]. Acta Phys. -Chim. Sin. 2024, 40(1), 2304018. doi: 10.3866/PKU.WHXB202304018

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202304018

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I1/2304018

图/表 9

Scheme 1

Fig 1

Fig 2

Fig 3

Table 1

Fig 4

Fig 5

Fig 6

Scheme 2

参考文献 52

1	Turner J. A. Science 2004, 305, 972. doi: 10.1126/science.1103197
2	Li Y. ; Zhang H. ; Xu T. ; Lu Z. ; Wu X. ; Wan P. ; Sun X. ; Jiang L. Adv. Funct. Mater. 2015, 25, 1737. doi: 10.1002/adfm.201404250
3	Abe J. O. ; Popoola A. P. I. ; Ajenifuja E. ; Popoola O. M. Int. J. Hydrog. Energy 2019, 44, 15072. doi: 10.1016/j.ijhydene.2019.04.068
4	Armaroli N. ; Balzani V. ChemSusChem 2011, 4, 21. doi: 10.1002/cssc.201000182
5	Ball M. ; Wietschel M. Int. J. Hydrog. Energy 2009, 34, 615. doi: 10.1016/j.ijhydene.2008.11.014
6	Fujishima A. ; Honda K. Nature 1972, 238, 37. doi: 10.1038/238037a0
7	Hashimoto K. ; Irie H. ; Fujishima A. Jpn. J. Appl. Phys. 2005, 44, 8269. doi: 10.1143/JJAP.44.8269
8	Li X. L. ; Yang G. Q. ; Li S. S. ; Xiao N. ; Li N. ; Gao Y. Q. ; Lv D. ; Ge L. Chem. Eng. J. 2020, 379, 122350. doi: 10.1016/j.cej.2019.122350
9	Li X. L. ; He R. B. ; Dai Y. J. ; Li S. S. ; Xiao N. ; Wang A. X. ; Gao Y. Q. ; Li N. ; Gao J. F. ; Zhang L. H. ; et al Chem. Eng. J. 2020, 400, 125474. doi: 10.1016/j.cej.2020.125474
10	Zhang Y. ; Yun S. ; Sun M. ; Wang X. ; Zhang L. ; Dang J. ; Yang C. ; Yang J. ; Dang C. ; Yuan S. J. Colloid Interface Sci. 2021, 604, 441. doi: 10.1016/j.jcis.2021.06.152
11	Cao S. ; Yu J. ; Wageh S. ; Al-Ghamdi A. A. ; Mousavi M. ; Ghasemi J. B. ; Xu F. J. Mater. Chem. A 2022, 10, 17174. doi: 10.1039/D2TA05181H
12	Wang L. ; Yang T. ; Peng L. ; Zhang Q. ; She X. ; Tang H. ; Liu Q. Chin. J. Catal. 2022, 43, 2720. doi: 10.1016/S1872-2067(22)64133-0
13	Gou X. ; Cheng F. ; Shi Y. ; Zhang L. ; Peng S. ; Chen J. ; Shen P. J. Am. Chem. Soc. 2006, 128, 7222. doi: 10.1021/ja0580845
14	Bai J. ; Chen W. ; Shen R. ; Jiang Z. ; Zhang P. ; Liu W. ; Li X. J. Mater. Sci. Technol. 2022, 112, 85. doi: 10.1016/j.jmst.2021.11.003
15	Gao B. ; Chen W. ; Liu J. ; An J. ; Wang L. ; Zhu Y. ; Sillanpää M. J. Photochem. Photobiol. A 2018, 364, 732. doi: 10.1016/j.jphotochem.2018.07.008
16	Song Y. ; Zhang J. ; Dong X. ; Li H. Energy Technol. 2021, 9 (5), 2100033. doi: 10.1002/ente.202100033
17	Peng S. ; Wu Y. ; Zhu P. ; Thavasi V. ; Ramakrishna S. ; Mhaisalkar S. G. J. Mater. Chem. 2011, 21, 15718. doi: 10.1039/C1JM12432C
18	Sun L. ; Qi Y. ; Jia C. J. ; Jin Z. ; Fan W. Nanoscale 2014, 6, 2649. doi: 10.1039/C3NR06104C
19	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
20	Xiao N. ; Li S. ; Li X. ; Ge L. ; Gao Y. ; Li N. Chin. J. Catal. 2020, 41, 642. doi: 10.1016/S1872-2067(19)63469-8
21	Ha Y. ; Shi L. ; Yan X. ; Chen Z. ; Li Y. ; Xu W. ; Wu R. ACS Appl. Mater. Interfaces 2019, 11, 45546. doi: 10.1021/acsami.9b13580
22	Luo S. ; Li X. ; Zhang B. ; Luo Z. ; Luo M. ACS Appl. Mater. Interfaces 2019, 11, 26891. doi: 10.1021/acsami.9b07100
23	Jiang J. ; Liu Q. ; Zeng C. ; Ai L. J. Mater. Chem. A 2017, 5, 16929. doi: 10.1039/C7TA04893
24	Zhao H. ; Yuan Z.-Y. Catal. Sci. Technol. 2017, 7, 330. doi: 10.1039/C6CY01719C
25	Li X. ; Gao Y. ; Li N. ; Ge L. Int. J. Hydrog. Energy 2022, 47, 27961. doi: 10.1016/j.ijhydene.2022.06.119
26	Guo Y. ; Tang J. ; Wang Z. ; Kang Y.-M. ; Bando Y. ; Yamauchi Y. Nano Energy 2018, 47, 494. doi: 10.1016/j.nanoen.2018.03.012
27	Zeng Z. ; Su Y. ; Quan X. ; Choi W. ; Zhang G. ; Liu N. ; Kim B. ; Chen S. ; Yu H. ; Zhang S. Nano Energy 2020, 69, 104409. doi: 10.1016/j.nanoen.2019.104409
28	Jiang K. ; Siahrostami S. ; Zheng T. ; Hu Y. ; Hwang S. ; Stavitski E. ; Peng Y. ; Dynes J. ; Gangisetty M. ; Su D. ; et al Energy Environ. Sci. 2018, 11, 893. doi: 10.1039/C7EE03245E
29	Gao J. ; Zhang F. ; Xue H. ; Zhang L. ; Peng Y. ; Li X. ; Gao Y. ; Li N. ; Lei G. Appl. Catal. B 2021, 281, 119509. doi: 10.1016/j.apcatb.2020.119509
30	Sun Z. ; Wang Y. ; Zhang L. ; Wu H. ; Jin Y. ; Li Y. ; Shi Y. ; Zhu T. ; Mao H. ; Liu J. ; et al Adv. Funct. Mater. 2020, 30 (15), 1910482. doi: 10.1002/adfm.201910482
31	Yu H. ; Fisher A. ; Cheng D. ; Cao D. ACS Appl. Mater. Interfaces 2016, 8, 21431. doi: 10.1021/acsami.6b04189
32	Chen Z. ; Wu R. ; Liu Y. ; Ha Y. ; Guo Y. ; Sun D. ; Liu M. ; Fang F. Adv. Mater. 2018, 30 (30), 1802011. doi: 10.1002/adma.201802011
33	Joya K. S. ; Sinatra L. ; AbdulHalim L. G. ; Joshi C. P. ; Hedhili M. N. ; Bakr O. M. ; Hussain I. Nanoscale 2016, 8, 9695. doi: 10.1039/C6NR00709K
34	Yang L. ; Shi L. ; Wang D. ; Lv Y. ; Cao D. Nano Energy 2018, 50, 691. doi: 10.1016/j.nanoen.2018.06.023
35	Zou H. ; Li G. ; Duan L. ; Kou Z. ; Wang J. Appl. Catal. B 2019, 259, 118100. doi: 10.1016/j.apcatb.2019.118100
36	Shen R. C. ; Hao L. ; Chen Q. ; Zheng Q. Q. ; Zhang P. ; Li X. Acta Phys. -Chim. Sin. 2022, 38 (7), 2110014.
	沈荣晨; 郝磊; 陈晴; 郑巧清; 张鹏; 李鑫; 物理化学学报, 2022, 38 (7), 2110014. doi: 10.3866/PKU.WHXB202110014
37	Li S. ; Gao Y. ; Li N. ; Ge L. ; Bu X. ; Feng P. Energy Environ. Sci. 2021, 14, 1897. doi: 10.1039/D0EE03697H
38	Lu Z. ; Wang J. ; Huang S. ; Hou Y. ; Li Y. ; Zhao Y. ; Mu S. ; Zhang J. ; Zhao Y. Nano Energy 2017, 42, 334. doi: 10.1016/j.nanoen.2017.11.004
39	Sun M. ; Li Z. ; Liu Y. ; Guo D. ; Xie Z. ; Huang Q. Int. J. Hydrog. Energy 2020, 45, 31892. doi: 10.1016/j.ijhydene.2020.08.213
40	Di T. ; Zhang L. ; Cheng B. ; Yu J. ; Fan J. J. Mater. Sci. Technol. 2020, 56, 170. doi: 10.1016/j.jmst.2020.03.032
41	Xie Y. ; Feng C. ; Guo Y. ; Li S. ; Guo C. ; Zhang Y. ; Wang J. Appl. Surf. Sci. 2021, 536, 147786. doi: 10.1016/j.apsusc.2020.147786
42	Wu K. ; Wu C. ; Bai W. ; Li N. ; Gao Y. ; Ge L. Colloids Surf. A 2023, 663, 131089. doi: 10.1016/j.colsurfa.2023.131089
43	Li X. ; Song S. ; Gao Y. ; Ge L. ; Song W. ; Ma T. ; Liu J. Small 2021, 17 (31), 2101315. doi: 10.1002/smll.202101315
44	Lu P. ; Yang Y. ; Yao J. ; Wang M. ; Dipazir S. ; Yuan M. ; Zhang J. ; Wang X. ; Xie Z. ; Zhang G. Appl. Catal. B 2019, 241, 113. doi: 10.1016/j.apcatb.2018.09.025
45	Liu H. ; Zhang J. ; Ao D. Appl. Catal. B 2018, 221, 433. doi: 10.1016/j.apcatb.2017.09.043
46	Zhu Y. ; Chen J. ; Shao L. ; Xia X. ; Liu Y. ; Wang L. Appl. Catal. B 2020, 268, 118744. doi: 10.1016/j.apcatb.2020.118744
47	Zhang Y. N. ; Gao M. ; Chen S. T. ; Wang H. Q. ; Huo P. W. Acta Phys. -Chim. Sin. 2023, 39 (6), 2211051.
	张怡宁; 高明; 陈松涛; 王会琴; 霍鹏伟; 物理化学学报, 2023, 39 (6), 2211051. doi: 10.3866/PKU.WHXB202211051
48	Wang S. ; Wang Y. ; Zhang S. L. ; Zang S. Q. ; Lou X. W. Adv. Mater. 2019, 31 (41), 1903404. doi: 10.1002/adma.201903404
49	Li Z. ; He H. ; Cao H. ; Sun S. ; Diao W. ; Gao D. ; Lu P. ; Zhang S. ; Guo Z. ; Li M. ; et al Appl. Catal. B 2019, 240, 112. doi: 10.1016/j.apcatb.2018.08.074
50	Li T. ; Luo G. ; Liu K. ; Li X. ; Sun D. ; Xu L. ; Li Y. ; Tang Y. Adv. Funct. Mater. 2018, 28 (51), 1805828. doi: 10.1002/adfm.201805828
51	Liu C. ; Yang Z. ; Li Y. RSC Adv. 2016, 6, 32983. doi: 10.1039/C6RA00984K
52	Tang J. Y. ; Yang D. ; Zhou W. G. ; Guo R. T. ; Pan W. G. ; Huang C. Y. J. Catal. 2019, 370, 79. doi: 10.1016/j.jcat.2018.12.009

Sample	H₂ evolution (μmol∙h⁻¹∙g⁻¹)	AQY (%)	Reference
WO₃@ZnIn₂S₄	8500	3.61	10
ZnIn₂S₄/g-C₃N₄/Ti₃C₂	2452.1	11.9	11
Ti₃C₂/ZnIn₂S₄/CdS	8930	0.79	12
g-C₃N₄/ZnIn₂S₄	2780	7.05	14
ZnIn₂S₄/NH₂-MIL-125(Ti)	2204.2	4.3	45
ZnIn₂S₄/CdS	3072	15.9	46
Ni-CNT/ZnIn₂S₄	12267	11.3	this work

[1]	吕宪伟, 丁信元, 龚家兴, 闫旭焕, 黄大勇, 耿建新, 袁忠勇. 轨道杂化在光催化与电催化中的研究进展[J]. 物理化学学报, 2026, 42(2): 100151 - .
[2]	刘宇, 李鹏飞, 刘翼泽, 孙再成. 碳点作为单一光催化剂的最新进展[J]. 物理化学学报, 2026, 42(2): 100167 - .
[3]	彭国强, 李秀艳, 李敏, 苏志博, 胡发露, 周国伟. 高效金属-有机框架的工程设计用于光催化CO₂还原[J]. 物理化学学报, 2026, 42(2): 100164 - .
[4]	张宇航, 李意, 曹玥晗, 帅英杰, 周宇, 周莹. Ir调控中间体生成类型抑制光催化甲烷转化中产物过氧化[J]. 物理化学学报, 2026, 42(2): 100173 - .
[5]	陈芸, 邓代洁, 徐丽, 朱兴旺, 李赫楠, 孙成明. 共价键调控电荷转移以实现自供能电化学传感平台对重金属离子的灵敏分析[J]. 物理化学学报, 2026, 42(1): 100144 - .
[6]	赵呈孝, 李昭霖, 吴东方, 杨小飞. SBA-15模板化共价三嗪框架增强光催化产氢[J]. 物理化学学报, 2026, 42(1): 100149 - .
[7]	葛成艳, 胡佳伟, 刘星雨, 宋玉玺, 刘超, 邹志刚. 自集成黑色NiO团簇与ZnIn₂S₄微球实现S型电子转移机制下光热辅助制氢[J]. 物理化学学报, 2026, 42(1): 100154 - .
[8]	陈轼逸, 付家龙, 裘建平, 常国菊, 郝仕油. 废弃医用口罩衍生的碳量子点增强BiOBr/g-C₃N₄ S型异质结光催化降解聚对苯二甲酸乙二醇酯(PET)[J]. 物理化学学报, 2026, 42(1): 100135 - .
[9]	黄火帅, 韦之栋, 严嘉玮, 池家晟, 苏千翔, 陈铭夏, 江治, 孙洋洲, 上官文峰. 揭示Zn_xCd_1−xS固溶体光催化析氢中的直接-间接带隙跃迁机制[J]. 物理化学学报, 2026, 42(1): 100141 - .
[10]	张凤英, 梅杨林, 蒋毓蔓, 郑申申, 郑凯波, 周莹. 瞬态吸收光谱在太阳能转化利用中的研究进展[J]. 物理化学学报, 2025, 41(9): 100118 - .
[11]	王文龙, 郝文韬, 何浪, 乔佳, 李宁, 陈朝秋, 覃勇. 碳量子点/TiO₂ S型异质结的能带和吸附工程促进光催化CO₂甲烷化[J]. 物理化学学报, 2025, 41(9): 100116 - .
[12]	洪佳楠, 许辰宇, 刘烟, 黎昌棋, 王梦琳, 张彦威. 通过边缘活性位点调控解析光热催化中析氢与二氧化碳还原的界面竞争[J]. 物理化学学报, 2025, 41(9): 100099 - .
[13]	韦梦兰, 欧晓霞, 王艺濛, 张梦圆, 滕飞, 王凯旋. S型异质结g-C₃N₄/Bi₂WO₆高效降解左氧氟沙星：性能、机理及降解路径[J]. 物理化学学报, 2025, 41(9): 100105 - .
[14]	李静萍, 严素定, 吴佳曦, 程强, 王楷. LiFePO₄改善无机/有机S型光催化剂的过氧化氢光合作用[J]. 物理化学学报, 2025, 41(9): 100104 - .
[15]	吴琦, 王长华, 李莹莹, 张昕彤. 增强g-C₃N₄@BN范德华异质结界面上的三重态电子转移增强光催化合成H₂O₂[J]. 物理化学学报, 2025, 41(9): 100107 - .

金属-有机骨架衍生的Ni-CNT/ZnIn₂S₄异质结用于光催化产氢及其电荷转移途径的确定

Identification of Charge Transfer Pathways in Metal-Organic Framework- Derived Ni-CNT/ZnIn₂S₄ Heterojunctions for Photocatalytic Hydrogen Evolution

RichHTML

PDF

赞