Study on the Photocatalytic Performance of Carbon Doped g-C3N4 Based on in situ Photomicrocalorimeter-fluorescence Spectrometry

doi:10.7503/cjcu20200292

Abstract

Abstract:

Carbon-doped graphite nitride（g-C₃N₄） was synthesized by adding tannic acid to urea precursor. X-ray photoelectron spectroscopy（XPS）， field emission scanning electron microscopy（FESEM）， X-ray diffractometer（XRD）， synchronous thermal analysis（TG-DSC） and other methods were used to characterize the morphology phase and valence components of carbon doped g-C₃N_4.The photocatalytic degradation mechanism of Rhodamine B was investigated by using UV-Vis and in situ photomicrocalorimeter-fluorescence spectrometry to obtain in situ thermodynamics/kinetic information and 3D fluorescence spectral information of the degradation of Rhodamine B by carbon doped g-C₃N₄.The results showed that， when the tannic acid concentration was ≤10 mg/mL， the carbon would replace nitrogen atoms in the unit structure of heptazine to form g-C₃N₄ skeleton carbon doping. When the tannic acid concentration is ≥20 mg/mL， the carbon deposition load on the surface of g-C₃N₄ in amorphous form forms amorphous carbon doping . The skeleton carbon doped g-C₃N₄to form π electrons effectively shorted the band gap width and reduced the photoelectron-hole recombination probability， showing excellent photocatalytic performance. The main active species of catalysis were h⁺ and ·O $2 -$ . The photocatalytic degradation process of carbon doped g-C₃N₄ can be divided into three processes： endothermic of light responds， the balance process of endothermic of light responds and exothermic of pollutant degradation， and stable exothermic. The intensity of fluorescence emission peak of Rhodamine B over skeleton carbon doped g-C₃N₄（C/N=0.844） decreased sharply within the illumination of 1000 s， its degradation rate reached 87.6%，which was 3.13 times and 1.95 times over original g-C₃N₄ and amorphous carbon doped g-C₃N₄， respectively. After illumination of 1000 s， the photodegradation of the ring and intermediates without fluorescent chromophores were dominated， which maintained a stable exothermic rate of （0.9799±0.5356） μJ/s with a pseudo-zero order process. This process was the rate-determining step. Therefore， Rhodamine B photocatalysis was a pseudo-zero-order process rather than a first order process．

Key words: g-C₃N₄, Doping, Photocatalyst, Photomicrocalorimeter, In situ fluorescence spectrum

CLC Number:

O642

TrendMD:

MA Xiangying, LIAO Yanjun, QIN Fanghong, YIN Yuanhao, HUANG Zaiyin, CHEN Qifeng. Study on the Photocatalytic Performance of Carbon Doped g-C₃N₄ Based on in situ Photomicrocalorimeter-fluorescence Spectrometry[J]. Chem. J. Chinese Universities, 2020, 41(11): 2526.

Figures/Tables 12

Sample	C/N	N1/N2	Area content of each characteristic peak of N₁_s(%)			Area content of each characteristic peak of C₁_s(%)
Sample	C/N	N1/N2	398.61 eV	400.29 eV	401.35 eV	284.60 eV	286.24 eV	287.76 eV
C₃N₄	0.754	6.613	46.16	6.98	3.13	4.09	0.75	37.59
C₃N₄C1	0.775	6.424	45.23	7.04	3.24	5.09	1.54	36.43
C₃N₄C2	0.800	5.904	42.63	7.22	4.87	6.38	2.41	34.97
C₃N₄C3	0.844	5.522	40.59	7.35	4.98	7.94	4.02	32.72
C₃N₄C4	0.987	3.680	33.78	9.45	5.01	9.54	7.89	30.19
C₃N₄C5	1.158	2.830	30.21	10.67	5.15	10.76	13.67	28.89
C₃N₄C6	1.276	2.307	26.11	11.32	5.26	11.24	17.08	26.17

Sample	E_g/eV	E_CB/eV	E_VB/eV	Sample	E_g/eV	E_CB/eV	E_VB/eV
C₃N₄	2.72	-1.14	1.58	C₃N₄C4	2.43	-0.995	1.435
C₃N₄C1	2.44	-1.00	1.44	C₃N₄C5	2.45	-1.005	1.445
C₃N₄C2	2.36	-0.96	1.40	C₃N₄C6	2.49	-1.025	1.465
C₃N₄C3	2.11	-0.835	1.275

Sample	(c₀-c)/c₀(%)	10² Reaction rate constant, k/min^-1	R²	Sample	(c₀-c)/c₀(%)	10² Reaction rate constant, k/min^-1	R²
RhB	0.35	-0.00575	0.9991	C₃N₄C3	89.07	-3.61	0.9917
C₃N₄	28.43	-0.544	0.9783	C₃N₄C4	49.56	-1.10	0.9916
C₃N₄C1	66.66	-1.85	0.9851	C₃N₄C5	46.39	-1.03	0.9893
C₃N₄C2	76.05	-2.47	0.9733	C₃N₄C6	44.14	-0.941	0.9720

Capture agent	Captured object	(c₀-c)/c₀(%)
Capture agent	Captured object	C₃N₄	C₃N₄C1	C₃N₄C2	C₃N₄C3	C₃N₄C4	C₃N₄C5	C₃N₄C6
Triethanolamine	h⁺	8.97	24.78	32.27	28.75	8.18	8.96	9.56
Benzoquinone	·O $2 -$	9.89	27.56	30.12	32.56	21.56	20.59	18.67
Isopropyl alcohol	·OH	15.21	45.54	54.56	63.68	25.82	23.78	21.34
Deionized water	Blank contrast	15.41	45.73	54.73	63.80	26.62	23.54	21.59

Capture agent	Captured object	(c₀-c)/c₀(%)
Capture agent	Captured object	C₃N₄	C₃N₄C1	C₃N₄C2	C₃N₄C3	C₃N₄C4	C₃N₄C5	C₃N₄C6
Triethanolamine	h⁺	8.97	24.78	32.27	28.75	8.18	8.96	9.56
Benzoquinone	·O $2 -$	9.89	27.56	30.12	32.56	21.56	20.59	18.67
Isopropyl alcohol	·OH	15.21	45.54	54.56	63.68	25.82	23.78	21.34
Deionized water	Blank contrast	15.41	45.73	54.73	63.80	26.62	23.54	21.59

Sample	Heat changes for different stages/mJ				R_cd/(μJ·s^-1)
Sample	ab	bc	cd	ad	R_cd/(μJ·s^-1)
C₃N₄	-94.73	73.24	1504.56	1483.07	0.5337 ± 0.3774
C₃N₄C1	-222.12	102.67	2820.52	2701.07	0.6748 ± 0.5487
C₃N₄C2	-253.41	123.67	3217.84	3088.10	0.8674 ± 0.4472
C₃N₄C3	-296.79	157.78	3768.74	3926.52	0.9799 ± 0.5356
C₃N₄C4	-192.38	98.89	2467.54	2374.05	0.6529 ± 0.4415
C₃N₄C5	-163.67	92.73	2089.93	2018.99	0.6207± 0.4319
C₃N₄C6	-147.08	87.54	1867.66	1808.12	0.6009 ± 0.4698

References 33

1	Wang X. C.， Maeda K.， Thomas A.， Takanabe K.， Xin G.， Carlsson J. M.， Domen K.， Antonietti1 M.， Nature Materials， 2009， 8（1）， 76―80
2	Su F. Z.， Mathew S. C.， Lipner G.， Fu X.， Antonietti M.， Blechert S.， Wang X.， J. Am. Chem. Soc.， 2010， 132， 16299―16301
3	Yan S. C.， Li Z. S.， Zou Z. G.， Langmuir， 2010， 26（6）， 3894―3901
4	Zhang J. S.， Wang B.， Wang X. C.， Prog. Chem. Beijing， 2014， 26（1）， 19―29
5	Wang P.， Huang B.， Dai Y.， Whangbo M. H.， Phys. Chem. Chem. Phys.， 2012， 14（28）， 9813―9829
6	Tonda S.， Kumar S.， Kandula S.， Shanker V.， J. Mater. Chem. A， 2014， 2（19）， 6772―6780
7	Li Y.， Xu X.， Zhang P.， Gong Y.， Li H. R.， Wang Y.， RSC Adv.， 2013， 3（27）， 10973―10982
8	Chang C.， Fu Y.， Hu M.， Wang C.， Shan G.， Zhu L.， Appl. Catal. B： Environ.， 2013， 142/143， 553―560
9	Xiao P.， Zhao Y. X.， Wang T.， Zhan Y.， Wang H.， Li J.， Thomas A.， Zhu J.， Chem. Eur. J.， 2014， 20（10）， 2872―2878
10	Zhang J. S.， Wang X. C.， International Conference on Clean Energy Science， 2011，4（3）， 675―678
11	Ma X. G.， Lv Y. H.， Xu J.， Liu Y.， Zhang R.， Zhu Y.， J. Phys. Chem. C， 2012， 116（44）， 23485―23493
12	Li J.， Shen B.， Hong Z.， Lin B.， Gao B.， Chen Y.， Chem. Commun. Royal Soc. Chem.， 2012，48（98）， 12017―12019
13	Zhang J.， Wu Y.， Xing M.， MLeghari S. A. K.， Sajjad S.， Energy Environ. Sci.， 2010， 3（6）， 715―726
14	Duan X. Y.， Zhao Y. J.， Yao R. H.， Solid State Commun.， 2008， 147， 194―197
15	Wang Q.， Chen C.， Ma W.， Zhu H.， Zhao J.， Chem. Eur. J.， 2009， 15（19）， 4765―4769
16	Zhang X.， Zhang L.， J. Phys. Chem. C，2010， 114（42）， 18198―18206
17	Xie K.， Umezawa N.， Zhang N.， Reunchan P.， Zhang Y.， Ye J.， Energy Environ. Sci.， 2011， 4（10）， 4211―4219
18	Li H. L.， Li F. P.， Wan Z. Y.， Jiao Y.C.， Liu Y.Y.， Wang P.， Zhang X.， Qin X.， Dai Y.， Huan B.， Appl. Catal. B： Environ.， 2018， 229（5）， 114―120
19	Zhao Z. W.， Sun Y. J.， Dong F.， Zhang Y.， Zhao H.， RSC Adv.， 2015， 5， 39549―39556
20	Tong Z. W.， Dong Y.， Yang D.， Zhao X.， Shi J.， Ding F.， Zou X.， Jiang Z.， Chem. Eng. J.， 2018，337， 312―321
21	Zhang J. H.， Wei M. J.， Wei Z. W.， Pan M.， Su C. Y.， Appl. Nano Mater.， 2020， 3（2）， 1010―1018
22	Thomas A.， Fischer A.， Goettmann F.， Antonietti M.， Müller J. O.， Schlögl R.， Carlsson J. M.， J. Mater. Chem.， 2008， 18， 4893―4908
23	Shiraishi Y.， Kanazawa S.， Kofuji Y.， Sakamoto H.， Ichikawa S.， Tanaka S.， Hirai T.， Angew. Chem. Int. Ed.， 2014， 53， 13454―13459
24	Schwinghammer K.， Mesch M. B.， Duppel V.， Ziegler C.， Senker J.， Lotsch B. V.， J. Am. Chem. Soc.， 2014， 136， 1730―1733
25	Dong F.， Zhao Z. W.， Xiong T.， Ni Z.， Zhang W.， Sun Y.， Ho W. K.， Appl. Mater. Interf.， 2013， 5， 11392―11401
26	Dong G. H.， Zhao K.， Zhang L. Z.， Chem. Commun.， 2012， 48， 6178―6180
27	Dong F.， Wang Z.， Sun Y.， Ho W. K.， Zhang H.， J. Colloid Interface Sci.， 2013，401， 70―79
28	He Y.， Zhang L.， Teng B.， Fan M.， Environ. Sci. Techn.， 2015，49（1）， 649―656
29	Zhang J. H.， Hou Y. J.， Wang S. J.， Zhu X.， Zhu C.， Wang Z.， Li C.， Jiang J.， Wang H.， Pan M.， Su C.， J. Mater. Chem. A， 2018， 6， 18252―18257
30	Li X. X.， Huang Z. Y.， Liu Z. J.， Diao K.， Fan G.， Huang Z.， Tan X.， Appl. Catal. B： Environ.， 2016， 181， 79―87
31	Qin J.， Huo J.， Zhang P.， Zeng J.， Wang T.， Zeng H.， Nanoscale， 2016， 8（4）， 2249―2259
32	Li J.， Wu D.， Iocozzia J.， Du H.， Liu X.， YuanY.， Zhou W.， Li Z.， Xue Z.，Lin Z.， Angew. Chem. Int. Ed.， 2019， 58， 1―6
33	Sousa L. A. E.， Beezer A. E.， Hansen L. D.， Clapham D.， Connor J. A.， Gaisford S.， J. Phys. Chem. B， 2012， 116（22）， 6356―6360

[1]	CHENG Qian, YANG Bolong, WU Wenyi, XIANG Zhonghua. S-doped Fe-N-C as Catalysts for Highly Reactive Oxygen Reduction Reactions [J]. Chem. J. Chinese Universities, 2022, 43(9): 20220341.
[2]	GONG Yanxi, WANG Jianbing, CHAI Buyu, HAN Yuanchun, MA Yunfei, JIA Chaomin. Preparation of Potassium Doped g-C₃N₄ Thin Film Photoanode and Its Application in Photoelectrocatalytic Oxidation of Diclofenac Sodium in Water [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220005.
[3]	SONG Youwei, AN Jiangwei, WANG Zheng, WANG Xuhui, QUAN Yanhong, REN Jun, ZHAO Jinxian. Effects of Ag，Zn，Pd-doping on Catalytic Performance of Copper Catalyst for Selective Hydrogenation of Dimethyl Oxalate [J]. Chem. J. Chinese Universities, 2022, 43(6): 20210842.
[4]	SONG Yingying, HUANG Lin, LI Qingsen, CHEN Limiao. Preparation of CuO/BiVO₄ Photocatalyst and Research on Carbon Dioxide Reduction [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220126.
[5]	SUN Xuefeng, RENAGUL Abdurahman, YANG Tongsheng, YANG Qianting. Synthesis and Luminescence Properties of Cr，In Co-doped Small Size MgGa₂O₄ Near-infrared Persistent Luminescence Nanoparticles [J]. Chem. J. Chinese Universities, 2022, 43(4): 20210850.
[6]	WANG Zumin, MENG Cheng, YU Ranbo. Doping Regulation in Transition Metal Phosphides for Hydrogen Evolution Catalysts [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220544.
[7]	XU Xiaolong, FANG Lining, LIU Changyu, LIU Minchao, JIA Jianbo. Preparation of Z-type g-C₃N₄/Pt/TiO₂ Nanotube Array Composite Electrode and Its Performance of Photoelectric Oxidation of Methanol [J]. Chem. J. Chinese Universities, 2021, 42(9): 2926.
[8]	HONG Yangyu, XING Hongzhu, BING Qiming, GAO Xuwen, QI Bin, CHEN Yakun, SU Tan, ZOU Bo. Synthesis and Fluorescence Properties of Novel Ce³⁺-doped Manganese Phosphite Open-framework Materials [J]. Chem. J. Chinese Universities, 2021, 42(9): 2725.
[9]	WU Yaqiang, LIU Siming, JIN Shunjin, YAN Yongqing, WANG Zhao, CHEN Lihua, SU Baolian. Synthesis of Zn-Doped NiCoP Catalyst with Porous Double-layer Nanoarray Structure and Its Electrocatalytic Properties for Hydrogen Evolution [J]. Chem. J. Chinese Universities, 2021, 42(8): 2483.
[10]	CHEN Mingsu, ZHANG Huiru, ZHANG Qi, LIU Jiaqin, WU Yucheng. First-principles Study on the Catalytic Effect of Co，P co-Doped MoS₂ in Lithium-sulfur Batteries [J]. Chem. J. Chinese Universities, 2021, 42(8): 2540.
[11]	YANG Xiaomei, WU Qiang, GUO Ru, YE Kaibo, XUE Ping, WANG Xiaozhong, LAI Xiaoyong. Ordered Mesoporous NiS-loaded CdS with Ultrathin Frameworks for Efficient Photocatalytic H₂ Production [J]. Chem. J. Chinese Universities, 2021, 42(5): 1581.
[12]	LI Dongping, LI Bin, LI Changheng, YU Xuegang, SHAN Yan, CHEN Kezheng. Synthesis and Enhanced Photocatalytic Activity of Ni₅P₄/g-C₃N₄ [J]. Chem. J. Chinese Universities, 2021, 42(4): 1292.
[13]	GUI Chen, WANG Haolin, SHAO Baixuan, YANG Yujing, XU Guangqing. Molten-salt-assistance Synthesis and Photocatalytic Hydrogen Evolution Performances of g-C₃N₄Nanostructures [J]. Chem. J. Chinese Universities, 2021, 42(3): 827.
[14]	LIU Zhigang, LI Jiabao, YANG Jian, MA Hao, WANG Chengyin, GUO Xin, WANG Guoxiu. Preparation of a Novel g-C₃N₄/Sn/N-doped Carbon Composite for Sodium Storage [J]. Chem. J. Chinese Universities, 2021, 42(2): 633.
[15]	CHEN Xiaoyu, YU Ranbo. Research Progress on Doping of Molybdenum Disulfide and Hydrogen Evolution Reaction [J]. Chem. J. Chinese Universities, 2021, 42(2): 475.

Study on the Photocatalytic Performance of Carbon Doped g-C₃N₄ Based on in situ Photomicrocalorimeter-fluorescence Spectrometry

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 33

Related Articles 15

Recommended Articles

Metrics

Comments