用于光降解气态硫化氢的TiO2/Bi4O5Br2阶梯型异质结的设计和制备: DFT计算、动力学、路径和机制

doi:10.1016/S1872-2067(24)60170-1

催化学报 ›› 2025, Vol. 68: 282-299.DOI: 10.1016/S1872-2067(24)60170-1

用于光降解气态硫化氢的TiO₂/Bi₄O₅Br₂阶梯型异质结的设计和制备: DFT计算、动力学、路径和机制

郝宝飞^a, Younes Ahmadi^a, Jan Szulejko^a, 张天豪^b^,^c, 路战胜^b^,^c, Ki-Hyun Kim^a^,^*()

^a汉阳大学土木与环境工程系, 首尔, 韩国
^b北京化工大学数理学院, 北京 100029, 中国
^c河南师范大学物理学院, 先进半导体与功能器件集成河南省重点实验室, 河南新乡 453007, 中国

收稿日期:2024-08-10 接受日期:2024-10-08 出版日期:2025-01-18 发布日期:2025-01-02
通讯作者: * 电子信箱: kkim61@hanyang.ac.kr (K.-H. Kim).
基金资助:
国家自然科学基金(12274118);河南省杰出外籍专家工作室(GZS2023007);河南省高等学校重点科研项目计划基础研究专项(22ZX013)

The design and fabrication of TiO₂/Bi₄O₅Br₂ step-scheme heterojunctions for the photodegradation of gaseous hydrogen sulfide: DFT calculation, kinetics, pathways, and mechanisms

Baofei Hao^a, Younes Ahmadi^a, Jan Szulejko^a, Tianhao Zhang^b^,^c, Zhansheng Lu^b^,^c, Ki-Hyun Kim^a^,^*()

^aDepartment of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-ro, Seoul 04763, Republic of Korea
^bSchool of Mathematics and Physics, Beijing University of Chemical Technology, Beijing 100029, China
^cHenan Key Laboratory of Advanced Semiconductor & Functional Device Integration, School of Physics, Henan Normal University, Xinxiang 453007, Henan, China

Received:2024-08-10 Accepted:2024-10-08 Online:2025-01-18 Published:2025-01-02
Contact: * E-mail: kkim61@hanyang.ac.kr (K.-H. Kim).
Supported by:
National Natural Science Foundation of China(12274118);Henan Center for Outstanding Overseas Scientists(GZS2023007);Special Project for Fundamental Research in University of Henan Province(22ZX013)

摘要/Abstract

摘要：

大气污染已成为威胁人类健康和破坏生态系统的重大问题. 其中, 硫化氢(H₂S)因其强烈的毒性、腐蚀性和刺鼻的气味而亟需得到有效解决. 尽管生物降解、化学吸附和物理吸附等传统方法已被用于去除H₂S, 但其降解效果仍不理想. 光催化降解H₂S因其环境友好和可持续发展的优点而受到越来越多的关注. 然而, 电子-空穴对(e^‒-h⁺)的重组现象严重抑制了光催化降解H₂S的效率.
为了解决上述问题, 本文通过原位水热法将TiO₂(P25)和Bi₄O₅Br₂薄片组合成TiO₂/Bi₄O₅Br₂ 异质结光催化剂(命名为x-TB-y: 其中x和y分别表示TiO₂:Bi₄O₅Br₂摩尔比和合成溶液的pH值), 并构建了阶梯结构(S-scheme). 通过X射线粉末衍射和傅里叶变换红外光谱(FT-IR)证明了TiO₂/Bi₄O₅Br₂复合材料的成功制备. 扫描电镜和透射电镜结果表明, 在TiO₂/Bi₄O₅Br₂复合材料中, TiO₂和Bi₄O₅Br₂分别呈现为球状和片装形貌. 利用X射线电子能谱(XPS)技术, 并结合密度泛函理论计算揭示了该材料的内部电场结构. 光电流强度曲线和电化学阻抗曲线表明, 相较于TiO₂和Bi₄O₅Br₂, 5-TB-9具有更强的载流子分离和传输能力. 通过紫外-可见漫反射光谱和莫特肖特基曲线表征了材料的导带和价带位置, 并结合电子自旋共振和原位XPS, 证实了TiO₂/Bi₄O₅Br₂中S-scheme的电荷转移途径. 优化后的异质结光催化剂5-TB-9, 在12 min内对在17 L密闭空间内10 ppm H₂S表出较高的去除效率(> 99%). 同时, 5-TB-9异质结催化剂具有较高的去除动力学速率(r: 0.7 mmol·h^‒1·g^‒1)、特定清洁空气输送率(SCADR: 5554 L·h^‒1·g^‒1)和量子产率(QY: 3.24 E-3 分子/光子). 此外, 研究了5-TB-9在不同催化剂用量(25‒150 mg)、H₂S浓度(5-20 ppm)、流速(100-160 L min^‒1)和相对湿度(20%-80%)下对H₂S的降解效果. 循环降解实验表明, 所制备的5-TB-9光催化剂在6次循环实验后仍保持较高的光催化降解活性, 在12 min内降解了92.0%的H₂S. 结合原位FT-IR和气相色谱-质谱结果, 研究了H₂S的降解机制, 结果表明H₂S直接转化生成了SO₄^2‒, 没有观察到中间产物.

综上, 本文证明了S-scheme TiO₂/Bi₄O₅Br₂光催化剂对有害H₂S气体的修复潜力, 为设计可持续的环境修复方案提供了参考.

关键词: 硫化氢去除, 光催化, S-scheme异质结, 可循环

Abstract:

It is a challenging task to efficiently convert deleterious hydrogen sulfide (H₂S) into less harmful products such as SO₄^2- species. In an effort to address such issue, a step-scheme (S-scheme) heterojunction photocatalyst has been built by concatenating TiO₂ (P25) and ultrathin Bi₄O₅Br₂ into TiO₂/Bi₄O₅Br₂ (namely, x-TB-y: x and y denote the molar ratio of TiO₂:Bi₄O₅Br₂ and pH value for solution-based synthesis, respectively) via in-situ hydrothermal method. The S-scheme charge transfer pathway in TB is confirmed by electron spin resonance and band structure analysis while experimental data and density functional theory calculations suggest the formation of an internal electric field to facilitate the separation and transfer of photoinduced charge carriers. Accordingly, the optimized heterojunction photocatalyst, i.e., 5-TB-9, showcases significantly high (> 99%) removal efficiency against 10 ppm H₂S in a 17 L chamber within 12 minutes (removal kinetic rate r: 0.7 mmol·h^-1·g^-1, specific clean air delivery rate SCADR: 5554 L·h^-1·g^-1, quantum yield QY: 3.24 E-3 molecules·photon^-1, and space-time yield STY: 3.24 E-3 molecules·photon^-1·mg^-1). Combined analysis of in-situ diffuse reflectance infrared Fourier transform adsorption spectra and gas chromatography-mass spectrometry allows to evaluate the mechanisms leading to the complete degradation of H₂S (i.e., into SO₄^2- without forming any intermediate species). This work demonstrates the promising remediation potential of an S-scheme TiO₂/Bi₄O₅Br₂ photocatalyst against hazardous H₂S gas for sustainable environmental remediation.

Key words: H₂S removal, Photocatalysis, S-scheme heterojunction, Recyclability

郝宝飞, Younes Ahmadi, Jan Szulejko, 张天豪, 路战胜, Ki-Hyun Kim. 用于光降解气态硫化氢的TiO₂/Bi₄O₅Br₂阶梯型异质结的设计和制备: DFT计算、动力学、路径和机制[J]. 催化学报, 2025, 68: 282-299.

Baofei Hao, Younes Ahmadi, Jan Szulejko, Tianhao Zhang, Zhansheng Lu, Ki-Hyun Kim. The design and fabrication of TiO₂/Bi₄O₅Br₂ step-scheme heterojunctions for the photodegradation of gaseous hydrogen sulfide: DFT calculation, kinetics, pathways, and mechanisms[J]. Chinese Journal of Catalysis, 2025, 68: 282-299.

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Order	AP code	HC code	Code of sample catalyst*	Composition	pH of synthesis solution	TiO₂ mass in TiO₂/Bi₄O₅Br₂ composites (mg)	Bi₄O₅Br₂ mass in TiO₂/Bi₄O₅Br₂ composites (mg)		Amount of sample loaded on HC (mg)
1	AP-T	HC-T	TiO₂	TiO₂	7	—	—	—	50
2	AP-B1	HC-B1	BOB-1	BiOBr	1	—	—	—	50
3	AP-B3	HC-B3	BOB-3	BiOBr	3	—	—	—	50
4	AP-B5	HC-B5	BOB-5	BiOBr	5	—	—	—	50
5	AP-B7	HC-B7	BOB-7	BiOBr	7	—	—	—	50
6	AP-B9	HC-B9	BOB-9	Bi₄O₅Br₂	9	—	—	—	50
7	AP-B11	HC-B11	BOB-11	Bi₄O₅Br₂	11	—	—	—	50
8	AP-1TB	HC-1TB	1-TB-9	Bi₄O₅Br₂, TiO₂	9	100	573	1.75	50
9	AP-3TB	HC-3TB	3-TB-9	Bi₄O₅Br₂, TiO₂	9	200	573	3.61	50
10	AP-5TB	HC-5TB	5-TB-9	Bi₄O₅Br₂, TiO₂	9	300	573	5.36	25−100
11	AP-7TB	HC-7TB	7-TB-9	Bi₄O₅Br₂, TiO₂	9	400	573	7.22	50
12	AP-9TB	HC-9TB	9-TB-9	Bi₄O₅Br₂, TiO₂	9	500	573	8.99	50

Order	AP code	HC code	Code of sample catalyst*	Composition	pH of synthesis solution	TiO₂ mass in TiO₂/Bi₄O₅Br₂ composites (mg)	Bi₄O₅Br₂ mass in TiO₂/Bi₄O₅Br₂ composites (mg)		Amount of sample loaded on HC (mg)
1	AP-T	HC-T	TiO₂	TiO₂	7	—	—	—	50
2	AP-B1	HC-B1	BOB-1	BiOBr	1	—	—	—	50
3	AP-B3	HC-B3	BOB-3	BiOBr	3	—	—	—	50
4	AP-B5	HC-B5	BOB-5	BiOBr	5	—	—	—	50
5	AP-B7	HC-B7	BOB-7	BiOBr	7	—	—	—	50
6	AP-B9	HC-B9	BOB-9	Bi₄O₅Br₂	9	—	—	—	50
7	AP-B11	HC-B11	BOB-11	Bi₄O₅Br₂	11	—	—	—	50
8	AP-1TB	HC-1TB	1-TB-9	Bi₄O₅Br₂, TiO₂	9	100	573	1.75	50
9	AP-3TB	HC-3TB	3-TB-9	Bi₄O₅Br₂, TiO₂	9	200	573	3.61	50
10	AP-5TB	HC-5TB	5-TB-9	Bi₄O₅Br₂, TiO₂	9	300	573	5.36	25−100
11	AP-7TB	HC-7TB	7-TB-9	Bi₄O₅Br₂, TiO₂	9	400	573	7.22	50
12	AP-9TB	HC-9TB	9-TB-9	Bi₄O₅Br₂, TiO₂	9	500	573	8.99	50

Order	AP code	Sample	X_H2S (%)	Quantum yield (molecules· photon^-1)	Quantum yield (t=0) (molecules·photon^-1)	Space time yield (molecules·phot on^-1·mg^-1)	Kinetic rate constant (second^-1)	Stream removal efficiency (%)	CADR (L·h^-1)	SCADR (L·h^-1·g^-1)	r_10% (at X = 10%) (mmol g^-1·h^-1)	r_max (mmol·g^-1· h^-1)
1	AP-T	TiO₂	31.3	1.01 E-3	8.58 E-3	2.02 E-5	4.78 E-4	0.37	27.6	552	1.22	0.22
2	AP-B1	BOB-1	34.3	1.11 E-3	5.92 E-3	2.22 E-5	5.76 E-4	0.44	34.2	682	0.65	0.24
3	AP-B3	BOB-3	41.0	1.33 E-3	5.92 E-3	2.66 E-5	8.15 E-4	0.62	48.6	972	0.7	0.29
4	AP-B5	BOB-5	54.7	1.77 E-3	5.51 E-3	3.54 E-5	1.14 E-3	0.87	68.4	1368	0.74	0.38
5	AP-B7	BOB-7	59.7	1.94 E-3	9.16 E-3	3.88 E-5	1.27 E-3	0.97	76.2	1524	1.47	0.42
6	AP-B9	BOB-9	81.0	2.62 E-3	1.25 E-2	5.24 E-5	2.37 E-3	1.81	143.4	2868	1.84	0.57
7	AP-B11	BOB-11	73.7	2.37 E-3	1.40 E-2	4.74 E-5	1.84 E-3	1.40	111	2220	2.3	0.52
8	AP-1TB	1-TB-9	94.7	3.06 E-3	1.88 E-2	6.12 E-5	3.67 E-3	2.87	224.4	4488	2.91	0.66
9	AP-3TB	3-TB-9	96.3	3.11 E-3	1.95 E-2	6.22 E-5	3.70 E-3	2.90	226.2	4524	1.97	0.67
10	AP-5TB	5-TB-9	100	3.24 E-3	1.51 E-2	6.48 E-5	4.53 E-3	3.55	277.2	5544	1.85	0.70
11	AP-7TB	7-TB-9	95.7	3.10 E-3	2.36 E-2	6.20 E-5	3.36 E-3	2.63	205.8	4116	3.02	0.67
12	AP-9TB	9-TB-9	92.7	3.00 E-3	1.79 E-2	6.00 E-5	3.32 E-3	2.60	202.8	4056	2.64	0.65

Order	AP code	Sample	X_H2S (%)	Quantum yield (molecules· photon^-1)	Quantum yield (t=0) (molecules·photon^-1)	Space time yield (molecules·phot on^-1·mg^-1)	Kinetic rate constant (second^-1)	Stream removal efficiency (%)	CADR (L·h^-1)	SCADR (L·h^-1·g^-1)	r_10% (at X = 10%) (mmol g^-1·h^-1)	r_max (mmol·g^-1· h^-1)
1	AP-T	TiO₂	31.3	1.01 E-3	8.58 E-3	2.02 E-5	4.78 E-4	0.37	27.6	552	1.22	0.22
2	AP-B1	BOB-1	34.3	1.11 E-3	5.92 E-3	2.22 E-5	5.76 E-4	0.44	34.2	682	0.65	0.24
3	AP-B3	BOB-3	41.0	1.33 E-3	5.92 E-3	2.66 E-5	8.15 E-4	0.62	48.6	972	0.7	0.29
4	AP-B5	BOB-5	54.7	1.77 E-3	5.51 E-3	3.54 E-5	1.14 E-3	0.87	68.4	1368	0.74	0.38
5	AP-B7	BOB-7	59.7	1.94 E-3	9.16 E-3	3.88 E-5	1.27 E-3	0.97	76.2	1524	1.47	0.42
6	AP-B9	BOB-9	81.0	2.62 E-3	1.25 E-2	5.24 E-5	2.37 E-3	1.81	143.4	2868	1.84	0.57
7	AP-B11	BOB-11	73.7	2.37 E-3	1.40 E-2	4.74 E-5	1.84 E-3	1.40	111	2220	2.3	0.52
8	AP-1TB	1-TB-9	94.7	3.06 E-3	1.88 E-2	6.12 E-5	3.67 E-3	2.87	224.4	4488	2.91	0.66
9	AP-3TB	3-TB-9	96.3	3.11 E-3	1.95 E-2	6.22 E-5	3.70 E-3	2.90	226.2	4524	1.97	0.67
10	AP-5TB	5-TB-9	100	3.24 E-3	1.51 E-2	6.48 E-5	4.53 E-3	3.55	277.2	5544	1.85	0.70
11	AP-7TB	7-TB-9	95.7	3.10 E-3	2.36 E-2	6.20 E-5	3.36 E-3	2.63	205.8	4116	3.02	0.67
12	AP-9TB	9-TB-9	92.7	3.00 E-3	1.79 E-2	6.00 E-5	3.32 E-3	2.60	202.8	4056	2.64	0.65

Order	AP code	Sample	Parameters	0 s	60 s	120 s	240 s	360 s	480 s	600 s
1	AP-5TB	5-TB-9	QY(t)	1.51 E-2	8.52 E-3	7.74 E-3	6.17 E-3	5.05 E-3	4.29 E-3	3.73 E-3
		5-TB-9	SQY(t)	1.51 E-3	1.09 E-3	1.29 E-3	1.7 E-3	2.33 E-3	3.8 E-3	1.0 E-3
2	AP-T	TiO₂	QY(t)	8.58 E-3	5.16 E-3	3.16 E-3	2.03 E-3	1.53 E-3	1.27 E-3	1.1 E-3
		TiO₂	SQY(t)	8.58 E-4	5.96 E-4	3.78 E-4	2.57 E-4	2.00 E-4	1.73 E-4	1.53 E-4

用于光降解气态硫化氢的TiO₂/Bi₄O₅Br₂阶梯型异质结的设计和制备: DFT计算、动力学、路径和机制

The design and fabrication of TiO₂/Bi₄O₅Br₂ step-scheme heterojunctions for the photodegradation of gaseous hydrogen sulfide: DFT calculation, kinetics, pathways, and mechanisms

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Metrics

Order	Photocatalyst mass (mg)	H₂S concentration (ppm)	Flow rate (L·min^-1)	Relative humidity (%)	X_H2S (%)	Kinetic rate constant (s^-1)
1	25	10	130	0	88.0	2.31 E-3
2	50	10	130	0	100	4.67 E-3
3	75	10	130	0	100	5.07 E-3
4	100	10	130	0	100	5.15 E-3
5	50	5	130	0	100	6.09 E-3
6	50	10	130	0	100	4.67 E-3
7	50	15	130	0	99.3	5.58 E-3
8	50	20	130	0	94.8	3.29 E-3
9	50	10	100	0	99.0	4.53 E-3
10	50	10	130	0	100	4.67 E-3
11	50	10	160	0	99.7	4.72 E-3
12	50	10	130	0	100	4.67 E-3
13	50	10	130	40	100	6.23 E-3
14	50	10	130	60	100	6.22 E-2
15	50	10	130	80	98.7	4.31 E-2

Order	Photocatalyst	Pollution	Light source	Reactor	Catalyst mass (mg)	Concentration (ppm)	Reaction duration (min)	Conversion (%)	r_max(mmol·g^-1·h^-1)	SCADR (L·h^-1·g^-1)	Quantum yield (molecules/ photon)	Space time yield (molecules/photon·mg)	Ref.
1	B-TiO₂/LDH	H₂S	Xenon lamp (300 w)	fixed-bed tube	100	100	60	96.4	—	—	2.07 E-6	2.14 E-8	[9]
2	Carbon-doped boron nitride	H₂S	LED lamp (40 W)	fixed-bed tube	40	20	80	99	—	—	2.24 E-6	5.60 E-8	[62]
3	CdS/C₃N₄	H₂S	Xenon lamp (300 w)	fixed-bed tube	50	10	30	99.9	—	—	2.58 E-6	5.16 E-8	[63]
4	SiO₂@α-Fe₂O₃@COF	H₂S	B-9 lamp (no mention of light intensity)	fixed-bed tube	40	20	120	95.4	—	—	—	—	[64]
5	CNFs@TiO₂ @MIL-100	H₂S	UV light (no mention of light intensity)	1.6 L chamber	—	200	140	93.5	—	—	—	—	[65]
6	Mn-TiO₂	H₂S	Two VUV lamps (4 W)	fixed-bed tube	1000	150	60	89.9	—	—	3.78 E-3	3.78 E-6	[66]
7	TiO₂@MIL-101	H₂S	UV light (no mention of light intensity)	1.6 L chamber	500	200	—	90	—	—	—	—	[67]
8	Pt@Cu-TiO₂	FA	0.98 W UV light	17 L chamber	50	0.5	10	100	0.042		1.94 E -4	3.88 E -6	[68]
9	TiO₂-diatomite	FA	250 W UV lamp	batch reactor	1000	0.79	180	90.9	3.5 E -3	160	8.91E-07	8.91E-10	[69]
10	rGO-TiO₂	FA	xenon lamp	stainless steel reactor	500	0.5	240	88.3	5.80 E-7	2. 96E-2	3.21 E-10	6.43 E-13	[70]
11	Pt-TiO₂	FA	visible light source	batch reactor	100	400	60	93.8	—	—	—	—	[71]
12	Pt@TiO₂	FA	18 W daylight lamp	reaction chamber	20	10	240	98.3	—	22.3	3.09 E-07	1.55 E-08	[72]
13	5-TB-9	H₂S	0.98 W UV light	17 L chamber	50	10	12	100	0.70	5544	3.24 E-3	6.48 E-5	this work

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