Citation: Qin Fanghong, Wan Ting, Qiu Jiangyuan, Wang Yihui, Xiao Biyuan, Huang Zaiyin. Temperature Effects on Photocatalytic Heat Changes and Kinetics via In Situ Photocalorimetry-Fluorescence Spectroscopy[J]. Acta Physico-Chimica Sinica, ;2020, 36(6): 190508. doi: 10.3866/PKU.WHXB201905087 shu

Temperature Effects on Photocatalytic Heat Changes and Kinetics via In Situ Photocalorimetry-Fluorescence Spectroscopy

Qin Fanghong ¹ ,
Wan Ting ² ,
Qiu Jiangyuan ^1,, ,
Wang Yihui ¹ ,
Xiao Biyuan ¹ ,
Huang Zaiyin ^1,3,,

1.
College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530008, P. R. China
2.
The Sixth Geological Bureau, Xiaogan 432000, Hubei Province, P. R. China
3.
Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Nanning 530008, P. R. China

Corresponding author: Qiu Jiangyuan, gxqiujiangyuan@yeah.net Huang Zaiyin, huangzaiyin@163.com
Received Date: 31 May 2019
Revised Date: 7 July 2019
Accepted Date: 17 July 2019
Available Online: 19 June 2019
Fund Project: the National Natural Science Foundation of China 21873022The project was supported by the National Natural Science Foundation of China (21873022, 21573048) and Innovation Project of Guangxi Graduate Education, China (gxun-chxzs2018062)Innovation Project of Guangxi Graduate Education, China gxun-chxzs2018062the National Natural Science Foundation of China 21573048

The thermodynamics and kinetics of photocatalytic processes provide the scientific foundation for the optimization of reaction conditions and establishment of reaction mechanisms. Because of the limited availability of techniques that can provide in situ thermodynamics coupled with spectral information during photo-driven processes, research regarding the thermodynamics of the photo-driven processes is rare and in-depth studies on their kinetics remain inadequate. Herein, a novel photocalorimetry-fluorescence spectroscopy system composed of a photocalorimeter and laser-induced fluorescence spectrometer based on a 405 nm laser was developed. This system could simultaneously monitor the thermal and spectral information during photocatalytic processes, providing a correlation between nonspecific thermodynamic and specific molecular fluorescence spectral results. A highly efficient, bionic Z-type g-C₃N₄@Ag@Ag₃PO₄ nano-composite photocatalyst was developed and characterized by field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). In situ thermodynamic and spectral kinetic information for Rhodamine B (RhB) degradation on g-C₃N₄@Ag@Ag₃PO₄ was obtained at five temperatures by synchronously monitoring the calorimetric and spectrometric results using the newly developed photocalorimetry-fluorescence spectroscopy system and the effects of temperature on various parameters were investigated. The catalytic decomposition comprised three stages at different temperatures: (ⅰ) photoresponse of RhB and photocatalyst, (ⅱ) competition between the endothermic photoresponse and exothermic RhB photodegradation, and (ⅲ) stable exothermic period of RhB photodegradation. The in situ heat flux and fluorescence spectra could be combined to estimate the concentration characteristics of the different photocatalytic reactions: (1) the spectral information suggested that the competitive endothermic and exothermic reactions followed first order kinetics, and the reaction rate constants (k) at five temperatures were calculated. The results also indicated that the degradation rate increased with increasing temperature. The activation energy at each temperature interval was determined, and yielded an average value of 23.82 kJ·mol⁻¹. (2) The calorimetric results revealed that the subsequent stable exothermic period was a pseudo-zero-order process. The exothermic rates at 283.15, 288.15, 293.15, 298.15, and 303.15 K were determined to be 0.4668 ± 0.3875, 0.5314 ± 0.3379, 0.5064 ± 0.3234, 0.5328 ± 0.3377, and 0.5762 ± 0.3452 μJ·s⁻¹, respectively. The novel photocalorimetry-fluorescence spectroscopy technique could concurrently obtain thermodynamic, thermo-kinetic, and molecular spectral information, allowing for the direct correlation of the thermodynamics, thermo-kinetics, and spectrokinetics with the underlying mechanisms of the reaction. This in situ technique integrated the thermal information with spectral information for improved understanding of the microscopic mechanisms of photo-driven processes, providing scientific support for the establishment of photothermal spectroscopy.
- g-C₃N₄@Ag@Ag₃PO₄,
- Photocatalysis,
- Photocalorimetry-fluorescence spectroscopy,
- Thermodynamics,
- Temperature effect
1. [1]
  Zhang, S. Y.; Bao, J. X.; Wu, B.; Zhong, L, S.; Sun, Y, H. Acta Phys. -Chim. Sin. 2019, 35 (9), 616. doi: 10.3866/PKU.WHXB201810002
2. [2]
  Gong, C.; Xiang, S. W.; Zhang, Z. Y.; Sun, L.; Ye, C. Q.; Lin, C. J. Acta Phys. -Chim. Sin. 2019, 35 (6), 616. doi: 10.3866/PKU.WHXB201805082
3. [3]
  Wang, W.; Li, G.; Xia, D.; An, T.; Zhao, H.; Wong, P. K. Environ. Sci: Nano 2017, 4 (4), 782. doi: 10.1039/C7EN00063D doi: 10.1039/C7EN00063D
4. [4]
  Fox, M. A; Dulay, M. T. Chem. Rev. 1993, 93 (1), 341. doi: 10.1021/cr00017a016 doi: 10.1021/cr00017a016
5. [5]
  Meng, F.; Liu, Y.; Wang, J.; Tan, X.; Sun, H.; Liu, S.; Wang, S. J. Colloid Interface Sci. 2018, 532, 321. doi: 10.1016/j.jcis.2018.07.131 doi: 10.1016/j.jcis.2018.07.131
6. [6]
  Zhang, L.; Mohamed, H. H.; Dillert, R.; Bahnemann, D. J. Photochem. Photobiol. C: Photochem. Rev. 2012, 13 (4), 263. doi: 10.1016/j.jphotochemrev.2012.07.002 doi: 10.1016/j.jphotochemrev.2012.07.002
7. [7]
  Velázquez, J. J.; Fernández-González, R.; Díaz, L.; Melián, E. P.; Rodríguez, V. D.; Núñez, P. J. Alloy. Compd. 2017, 721, 405. doi: 10.1016/j.jallcom.2017.05.314 doi: 10.1016/j.jallcom.2017.05.314
8. [8]
  Zhang, T.; Pan, G.; Zhou, Q. J. Environ. Sci. 2016, 42, 126. doi: 10.1016/j.jes.2015.05.008 doi: 10.1016/j.jes.2015.05.008
9. [9]
  Liu, S, X., Liu, H. Foundation and Application of Photocatalysis and Photoelectricity; Chemical Industry Press: Beijing, 2006; pp. 59–64.
10. [10]
  Xiao, M.; Huang, Z. Y.; Tang, H. F.; Lu, S. T.; Liu, C. Acta Phys.-Chim. Sin. 2017, 33 (2), 339. doi: 10.3866/PKU.WHXB201611092
11. [11]
  Zhang, J. W.; Wang, S.; Liu, F. S.; Fu, X. J.; Ma, G. Q.; Hou, M. S.; Tang, Z. Acta Phys. -Chim. Sin. 2019, 35 (8), 885. doi: 10.3866/PKU.WHXB201812022
12. [12]
  Ohtani B. Phys. Chem. Chem. Phys. 2014, 16 (5), 1788. doi: 10.1039/C3CP53653J doi: 10.1039/C3CP53653J
13. [13]
  Ghasemi, Z.; Younesi, H.; Zinatizadeh, A. A. J. Taiwan Inst. Chem. E 2016, 65, 357. doi: 10.1016/j.jtice.2016.05.039 doi: 10.1016/j.jtice.2016.05.039
14. [14]
  Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.; Horiuchi, Y.; Anpo, M.; Bahnemann, D. W. Chem. Rev. 2014, 114 (19), 9919. doi: 10.1021/cr5001892 doi: 10.1021/cr5001892
15. [15]
  Lee, K. M.; Hamid, S. B. A.; Lai, C. W. J. Nanomater. 2015, 2015, 9. doi: 10.1155/2015/940857 doi: 10.1155/2015/940857
16. [16]
  Bauchard, E.; This, H. Talanta 2015, 131, 335. doi: 10.1016/j.talanta.2014.07.097 doi: 10.1016/j.talanta.2014.07.097
17. [17]
  Gondal, M. A.; Hameed, A.; Yamani, Z. H.; Arfaj, A. Chem. Phys. Lett. 2004, 392 (4–6), 372. doi: 10.1016/j.cplett.2004.05.092 doi: 10.1016/j.cplett.2004.05.092
18. [18]
  Mikko, M.; Shane, M. P.; Enrico, B.; Alexander, L.; Martijn, A. Z.; Filipp, F. Chem. Sci. 2017, 8 (3), 2179. doi: 10.1039/C6SC04378J doi: 10.1039/C6SC04378J
19. [19]
  Brady, G. A.; Halloran, J. W.; J. Mater. Sci. 1998, 33 (18), 4551. doi: 10.1023/A:1004416705140 doi: 10.1023/A:1004416705140
20. [20]
  Li, X. X.; Fan, G. C.; Ma, Z.; Tan, X. C.; Huang, Z. Y. Sci. China Chem. 2014, 10, 1576. doi: 10.1360/N032013-00066
21. [21]
  Li, X. X.; Huang, Z. Y.; Fan, G. C.; Wu, Y. N.; Tan, X. C. Chem. J. Chin. Univ. 2014, 7, 1480. doi: 10.7503/cjcu20140176
22. [22]
  Li, X, X.; Huang, Z.; Liu, Z.; Diao, K.; Fan, G.; Huang, Z.; Tan, X. Appl. Catal. B-Environ. 2016, 181, 79. doi: 10.1016/j.apcatb.2015.07.036 doi: 10.1016/j.apcatb.2015.07.036
23. [23]
  Li, X. X.; Wan, T.; Qiu, J. Y.; Wei, H.; Qin, F. H.; Wang, Y. H.; Huang, Z. Y.; Tan, X. C. Appl. Catal. B-Environ. 2017, 217, 591. doi: 10.1016/j.apcatb.2017.05.086 doi: 10.1016/j.apcatb.2017.05.086
24. [24]
  Wan, T.; Li, X. X.; Huang, Z. Y.; Qiu, J. Y.; Zuo, C.; Tan, X. C. Chem. J. Chin. Univ. 2017, 38 (12), 2226. doi: 10.7503/cjcu20170371
25. [25]
  Chen, Y.; Huang, W.; He, D.; Situ, Y.; Huang, H. ACS Appl. Mater. Inter. 2014, 6 (16), 14405. doi: 10.1021/am503674e doi: 10.1021/am503674e
26. [26]
  Fu, X, C.; Shen, W, X.; Yao, T, Y. Physical Chemistry, 5th ed.; Higher Education Press: Beijing, 2006; pp. 163–201.
1. [1]
  Changjun You , Chunchun Wang , Mingjie Cai , Yanping Liu , Baikang Zhu , Shijie Li . 引入内建电场强化BiOBr/C₃N₅ S型异质结中光载流子分离以实现高效催化降解微污染物. Acta Physico-Chimica Sinica, 2024, 40(11): 2407014-. doi: 10.3866/PKU.WHXB202407014
2. [2]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
3. [3]
  Yingqi BAI , Hua ZHAO , Huipeng LI , Xinran REN , Jun LI . Perovskite LaCoO₃/g-C₃N₄ heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 480-490. doi: 10.11862/CJIC.20240259
4. [4]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . 熔融中间体运输导向合成富氨基g-C₃N₄纳米片用于高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-. doi: 10.3866/PKU.WHXB202406021
5. [5]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
6. [6]
  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
7. [7]
  Jianyin He , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . ZnCoP/CdLa₂S₄肖特基异质结的构建促进光催化产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2404030-. doi: 10.3866/PKU.WHXB202404030
8. [8]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . 两步焙烧法制备大比表面积和结晶性增强超薄g-C₃N₄纳米片及其高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-. doi: 10.3866/PKU.WHXB202406019
9. [9]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(VI) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-. doi: 10.3866/PKU.WHXB202309020
10. [10]
  Shijie Li , Ke Rong , Xiaoqin Wang , Chuqi Shen , Fang Yang , Qinghong Zhang . Design of Carbon Quantum Dots/CdS/Ta₃N₅ S-Scheme Heterojunction Nanofibers for Efficient Photocatalytic Antibiotic Removal. Acta Physico-Chimica Sinica, 2024, 40(12): 2403005-. doi: 10.3866/PKU.WHXB202403005
11. [11]
  Xin Zhou , Zhi Zhang , Yun Yang , Shuijin Yang . A Study on the Enhancement of Photocatalytic Performance in C/Bi/Bi₂MoO₆ Composites by Ferroelectric Polarization: A Recommended Comprehensive Chemical Experiment. University Chemistry, 2024, 39(4): 296-304. doi: 10.3866/PKU.DXHX202310008
12. [12]
  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. Acta Physico-Chimica Sinica, 2025, 41(4): 100031-. doi: 10.3866/PKU.WHXB202402016
13. [13]
  Yang Xia , Kangyan Zhang , Heng Yang , Lijuan Shi , Qun Yi . 构建双通道路径增强iCOF/Bi₂O₃ S型异质结在纯水体系中光催化合成H₂O₂性能. Acta Physico-Chimica Sinica, 2024, 40(11): 2407012-. doi: 10.3866/PKU.WHXB202407012
14. [14]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
15. [15]
  Xi YANG , Chunxiang CHANG , Yingpeng XIE , Yang LI , Yuhui CHEN , Borao WANG , Ludong YI , Zhonghao HAN . Co-catalyst Ni₃N supported Al-doped SrTiO₃: Synthesis and application to hydrogen evolution from photocatalytic water splitting. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 440-452. doi: 10.11862/CJIC.20240371
16. [16]
  Kexin Dong , Chuqi Shen , Ruyu Yan , Yanping Liu , Chunqiang Zhuang , Shijie Li . Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag₃PO₄/C₃N₅ Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation. Acta Physico-Chimica Sinica, 2024, 40(10): 2310013-. doi: 10.3866/PKU.WHXB202310013
17. [17]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
18. [18]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
19. [19]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
20. [20]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(1039)
HTML views(165)

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