Citation: CHEN Qi, ZHOU Yu, ZHU Ji-Xiu, LIANG Tian-Tian, HUANG Rong-Bin, CHEN Ai-Min. Photocatalytic Synthesis of Ammonia over Fe₂O₃/ZnO with Rich Surface Oxygen Vacancy[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(3): 426-434. doi: 10.11862/CJIC.2020.063 shu

Photocatalytic Synthesis of Ammonia over Fe₂O₃/ZnO with Rich Surface Oxygen Vacancy

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Corresponding author: HUANG Rong-Bin, huangrb@zjut.edu.cn CHEN Ai-Min, amchen@zjut.edu.cn
Received Date: 17 August 2019
Revised Date: 3 December 2019

Figures(13)

Photocatalytic synthesis of ammonia is a sustainable and energy-saving synthetic ammonia technology. Rich oxygen vacancies and heterostructures are important to increase the photocatalytic nitrogen to ammonia. We synthesized Fe₂O₃/ZnO nanocomposites by solvothermal method using ethylene glycol as the reducing agent. X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR), UV-Vis DRS, photoluminescence (PL) and photocurrent (PC) were used to characterize the Fe₂O₃/ZnO catalysts. The performance of photocatalytic synthesis of ammonia by Fe₂O₃/ZnO catalysts was tested at room temperature. The results show that heterostructure was formed between ZnO nanorods and Fe₂O₃ nanoparticles while abundant surface oxygen vacancies were produced over the Fe₂O₃/ZnO catalysts. Fe₂O₃ nanoparticles not only provide rich N₂ chemical adsorption sites, but also promote the light absorption of ZnO in the visible region. The introduction of Fe₂O₃ reduces the concentration of bulk oxygen vacancies and inhibits the recombination of photogenerated electrons and holes. The 4%Fe₂O₃/ZnO catalyst exhibited enhanced photocatalytic nitrogen fixation efficiency with a NH₃ rate of 2 059 μmol·L^-1·g^-1·h^-1 with better stability. The high catalytic efficiency is attributed to the enhancement of visible light absorption, the activation of nitrogen molecules on surface oxygen vacancies and Fe³⁺ active sites, and the high separation efficiency of photogenerated electrons and holes.
- photocatalytic synthesis of ammonia,
- zinc oxide,
- oxygen vacancy,
- heterojunction,
- iron oxide
1. [1]
  Skulason E, Bligaard T, Gudmundsdottir S, et al. Phys. Chem. Chem. Phys., 2012, 14(3):1235-1245 doi: 10.1039/C1CP22271F
2. [2]
  Service R F.. Science, 2014, 345(6197):610 doi: 10.1126/science.345.6197.610
3. [3]
  Iwamoto M, Akiyama M, Aihara K, et al. ACS Catal., 2017, 7 (10):6924-6929 doi: 10.1021/acscatal.7b01624
4. [4]
  Wang P K, Chang F, Gao W B, et al. Nat. Chem., 2017, 9(1): 64-70 doi: 10.1038/nchem.2595
5. [5]
  Liu J, Kelley M S, Wu W, et al. Proc. Natl. Acad. Sci. U.S.A., 2016, 113:5530-5535 doi: 10.1073/pnas.1605512113
6. [6]
  LIU Jian, XIAO Yao, HU Wen-Juan, et al. Prog. Chem., 2018, 30(4):325-337
7. [7]
  Singh A R, Rohr B A, Schwalbe J A, et al. ACS Catal., 2017, 7(1):706-709 doi: 10.1021/acscatal.6b03035
8. [8]
  Ali M, Zhou F, Chen K, et al. Nat. Commun., 2016, 7:11335 doi: 10.1038/ncomms11335
9. [9]
  Banerjee A, Yuhas B D, Margulies E A, et al. J. Am. Chem. Soc., 2015, 137(5):2030-2034 doi: 10.1021/ja512491v
10. [10]
  Yang J H, Guo Y Z, Jiang R B, et al. J. Am. Chem. Soc., 2018, 140(27):8497-8508 doi: 10.1021/jacs.8b03537
11. [11]
  Hirakawa H, Hashimoto M, Shiraishi Y, et al. ACS Catal., 2017, 7(5):3713-3720 doi: 10.1021/acscatal.7b00611
12. [12]
  GAO Xiao-Ming, SHANG Yan-Yan, LIU Li-Bo, et al. Chinese J. Inorg. Chem., 2019, 35(4):580-588
13. [13]
  Rani B J, Ravi G, Yuvakkumar R, et al. Renewable Energy, 2019, 133:566-574 doi: 10.1016/j.renene.2018.10.067
14. [14]
  Li Y S, Wei G T, Shao L H, et al. J. Cleaner Prod., 2019, 207: 717-727 doi: 10.1016/j.jclepro.2018.10.051
15. [15]
  Medford A J, Hatzell M C.. ACS Catal., 2017, 7(4):2624-2643 doi: 10.1021/acscatal.7b00439
16. [16]
  Wang S Y, Ichihara F, Pang H, et al. Adv. Funct. Mater., 2018, 28(50):1803309 doi: 10.1002/adfm.201803309
17. [17]
  Li H, Mao C, Shang H, et al. Nanoscale, 2018, 10(33):15429 -15435 doi: 10.1039/C8NR04277B
18. [18]
  Yan T, Tian J, Guan W, et al. Appl. Catal. B: Environ., 2017, 202:84-94 doi: 10.1016/j.apcatb.2016.09.017
19. [19]
  Chen X Z, Li N, Kong Z Z, et al. Mater. Horiz., 2018, 5(1):9- 27
20. [20]
  Xiong Z, Lei Z, Xu Z W, et al. J. CO2 Util., 2017, 18:53-61 doi: 10.1016/j.jcou.2017.01.013
21. [21]
  Yu W L, Xu D F, Peng T Y.. J. Mater. Chem. A, 2015, 3(39): 19936-19947 doi: 10.1039/C5TA05503B
22. [22]
  Kegel J, Povey I M, Pemble M E.. Nano Energy, 2018, 54: 409-428 doi: 10.1016/j.nanoen.2018.10.043
23. [23]
  Lamouchi A, Ben Assaker I, Chtourou R.. Appl. Surf. Sci., 2019, 478:937-945 doi: 10.1016/j.apsusc.2019.02.030
24. [24]
  Janet C M, Navaladian S, Viswanathan B, et al. J. Phys. Chem. C, 2010, 114(6):2622-2632 doi: 10.1021/jp908683x
25. [25]
  Long X F, Li F, Gao L L, et al. ChemSusChem, 2018, 11: 4094-4101 doi: 10.1002/cssc.201801828
26. [26]
  Wang J, Xia Y, Dong Y, et al. Appl. Catal. B: Environ., 2016, 192:8-16 doi: 10.1016/j.apcatb.2016.03.040
27. [27]
  Dong G, Ho W, Wang C.. J. Mater. Chem. A, 2015, 3:23435- 23441 doi: 10.1039/C5TA06540B
28. [28]
  Yang X, Nash J, Anibal J, et al. J. Am. Chem. Soc., 2018, 140:13387-13391 doi: 10.1021/jacs.8b08379
29. [29]
  Meng Q, Lv C, Sun J, et al. Appl. Catal. B: Environ., 2019, 256:117781-117790 doi: 10.1016/j.apcatb.2019.117781
30. [30]
  Yin, X, Li X, Liu H, et al. Nano Energy, 2018, 49:489497
31. [31]
  Zhao H, Wang J, Chen C, et al. RSC Adv., 2016, 6(69): 64258-64265 doi: 10.1039/C6RA11352D
32. [32]
  Ye L, Han C, Ma Z, et al. Chem. Eng. J., 2017, 307:311-318 doi: 10.1016/j.cej.2016.08.102
33. [33]
  Xu C, Qiu P, Li L, et al. ACS Appl. Mater. Interfaces, 2018, 10(30):25321-25328 doi: 10.1021/acsami.8b05925
34. [34]
  Li L, Wang Y, Vanka S, et al. Angew. Chem., 2017, 129: 8827-8831 doi: 10.1002/ange.201703301
35. [35]
  Zhang Y, Di J, Ding P, et al. J. Colloid Interface Sci., 2019, 553:530-539 doi: 10.1016/j.jcis.2019.06.012
36. [36]
  Hirakawa H, Hashimoto M, Shiraishi Y, et al. J. Am. Chem. Soc., 2017, 139(45):10929-10936
37. [37]
  Xu H, Wang Y, Dong X, et al. Appl. Catal. B: Environ., 2019, 257:117932 doi: 10.1016/j.apcatb.2019.117932
38. [38]
  Di J, Xia J, Chisholm M F, et al. Adv. Mater., 2019, 31(28): 1807576 doi: 10.1002/adma.201807576
39. [39]
  Bianca L G, Rita S T, Ramón M F D, et al. Appl. Surf. Sci., 2017, 392:503-513 doi: 10.1016/j.apsusc.2016.09.073
40. [40]
  Park W I, Yi G C, Kim M Y, et al. J. Adv. Mater., 2002, 14 (24):1841-1843 doi: 10.1002/adma.200290015
41. [41]
  Li C C, Wang T, Zhao Z J, et al. Angew. Chem. Int. Ed., 2018, 57(19):5278-5282 doi: 10.1002/anie.201713229
42. [42]
  Gao X, Wen Y J, Qu D, et al. ACS Sustainable Chem. Eng., 2018, 6:5342-534 doi: 10.1021/acssuschemeng.8b00110
43. [43]
  Kumar P S, Selvakumar M, Babu S G, et al. J. Alloys Compd., 2017, 701:562-573 doi: 10.1016/j.jallcom.2017.01.126
44. [44]
  Peng Y K, Tsang S C E.. Nano Today, 2018, 18:15-34 doi: 10.1016/j.nantod.2017.12.011
1. [1]
  Zijian Jiang , Yuang Liu , Yijian Zong , Yong Fan , Wanchun Zhu , Yupeng Guo . Preparation of Nano Zinc Oxide by Microemulsion Method and Study on Its Photocatalytic Activity. University Chemistry, 2024, 39(5): 266-273. doi: 10.3866/PKU.DXHX202311101
2. [2]
  Deyun Ma , Fenglan Liang , Qingquan Xue , Yanping Liu , Chunqiang Zhuang , Shijie Li . Interfacial engineering of Cd_0.5Zn_0.5S/BiOBr S-scheme heterojunction with oxygen vacancies for effective photocatalytic antibiotic removal. Acta Physico-Chimica Sinica, 2025, 41(12): 100190-0. doi: 10.1016/j.actphy.2025.100190
3. [3]
  Chunchun Wang , Changjun You , Ke Rong , Chuqi Shen , Fang Yang , Shijie Li . An S-Scheme MIL-101(Fe)-on-BiOCl Heterostructure with Oxygen Vacancies for Boosting Photocatalytic Removal of Cr(Ⅵ). Acta Physico-Chimica Sinica, 2024, 40(7): 2307045-0. doi: 10.3866/PKU.WHXB202307045
4. [4]
  Ruifeng CHEN , Chao XU , Jianting JIANG , Tianshe YANG . Gold nanorod/zinc oxide/mesoporous silica nanoplatform: A triple-modal platform for synergistic anticancer therapy. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2272-2282. doi: 10.11862/CJIC.20250117
5. [5]
  Yachao HUANG , Chuanwang ZENG , Guiyong LIU , Jinming ZENG , Chao LIU , Xiaopeng QI . Oxygen vacancies and phosphorus doping enhanced metal-organic framework derived nitrogen-doped carbon-coated Co₃O₄ bifunctional electrocatalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2251-2260. doi: 10.11862/CJIC.20250133
6. [6]
  Bowen Liu , Jianjun Zhang , Han Li , Bei Cheng , Chuanbiao Bie . MOF-derived ZnO/PANI S-scheme heterojunction for efficient photocatalytic phenol mineralization coupled with H₂O₂ generation. Acta Physico-Chimica Sinica, 2025, 41(10): 100121-0. doi: 10.1016/j.actphy.2025.100121
7. [7]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
8. [8]
  Yu Guo , Zhiwei Huang , Yuqing Hu , Junzhe Li , Jie Xu . Recent Advances in Iron-based Heterostructure Anode Materials for Sodium Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(3): 100022-0. doi: 10.3866/PKU.WHXB202311015
9. [9]
  Weicheng Feng , Jingcheng Yu , Yilan Yang , Yige Guo , Geng Zou , Xiaoju Liu , Zhou Chen , Kun Dong , Yuefeng Song , Guoxiong Wang , Xinhe Bao . Regulating the High Entropy Component of Double Perovskite for High-Temperature Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(6): 2306013-0. doi: 10.3866/PKU.WHXB202306013
10. [10]
  Shi-Yu Lu , Wenzhao Dou , Jun Zhang , Ling Wang , Chunjie Wu , Huan Yi , Rong Wang , Meng Jin . Amorphous-Crystalline Interfaces Coupling of CrS/CoS₂ Few-Layer Heterojunction with Optimized Crystallinity Boosted for Water-Splitting and Methanol-Assisted Energy-Saving Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(8): 2308024-0. doi: 10.3866/PKU.WHXB202308024
11. [11]
  Yu Wang , Shoulei Zhang , Tianming Lv , Yan Su , Xianyu Liu , Fuping Tian , Changgong Meng . Introduce a Comprehensive Inorganic Synthesis Experiment: Synthesis of Nano Zinc Oxide via Microemulsion Using Waste Soybean Oil. University Chemistry, 2024, 39(7): 316-321. doi: 10.3866/PKU.DXHX202311035
12. [12]
  Qishen Wang , Changzhao Chen , Mengqing Li , Lingmin Wu , Kai Dai . Lignin derived carbon quantum dots and oxygen vacancies coregulated S-scheme LCQDs/Bi₂WO₆ heterojunction for photocatalytic H₂O₂ production. Acta Physico-Chimica Sinica, 2025, 41(11): 100147-0. doi: 10.1016/j.actphy.2025.100147
13. [13]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
14. [14]
  Qinjin DAI , Shan FAN , Pengyang FAN , Xiaoying ZHENG , Wei DONG , Mengxue WANG , Yong ZHANG . Performance of oxygen vacancy-rich V-doped MnO₂ for high-performance aqueous zinc ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 453-460. doi: 10.11862/CJIC.20240326
15. [15]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
16. [16]
  Qiang Cheng , Jingping Li , Zhendong Ke , Jiaming Li , Kai Wang . Advanced oxidation technology synergistic photothermal degradation of antibiotics over inorganic/organic S-scheme heterojunction. Acta Physico-Chimica Sinica, 2026, 42(5): 100187-0. doi: 10.1016/j.actphy.2025.100187
17. [17]
  Jia Wang , Qing Qin , Zhe Wang , Xuhao Zhao , Yunfei Chen , Liqiang Hou , Shangguo Liu , Xien Liu . P-Doped Carbon-Supported Zn_xP_yO_z for Efficient Ammonia Electrosynthesis under Ambient Conditions. Acta Physico-Chimica Sinica, 2024, 40(3): 2304044-0. doi: 10.3866/PKU.WHXB202304044
18. [18]
  Minna Ma , Yujin Ouyang , Yuan Wu , Mingwei Yuan , Lijuan Yang . Green Synthesis of Medical Chemiluminescence Reagents by Photocatalytic Oxidation. University Chemistry, 2024, 39(5): 134-143. doi: 10.3866/PKU.DXHX202310093
19. [19]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-0. doi: 10.3866/PKU.WHXB202407005
20. [20]
  Jiali Lei , Juan Wang , Wenhui Zhang , Guohong Wang , Zihui Liang , Jinmao Li . TiO₂/CdIn₂S₄ S-scheme heterojunction photocatalyst promotes photocatalytic hydrogen evolution coupled vanillyl alcohol oxidation. Acta Physico-Chimica Sinica, 2025, 41(12): 100174-0. doi: 10.1016/j.actphy.2025.100174

Get Citation

PDF

XML

Metrics

PDF Downloads(44)
Abstract views(3798)
HTML views(937)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Photocatalytic Synthesis of Ammonia over Fe2O3/ZnO with Rich Surface Oxygen Vacancy

Metrics

通讯作者: 陈斌, bchen63@163.com

Photocatalytic Synthesis of Ammonia over Fe₂O₃/ZnO with Rich Surface Oxygen Vacancy