铜掺杂与氮化碳复合氧化锌材料结构和二氧化氮气体传感性质的密度泛函理论计算

doi:10.6023/A23060312

摘要/Abstract

氮氧化物已引发环境污染和危害人类健康等诸多问题. 然而, 氧化锌基传感器件在监测时存在响应和恢复时间长、核心材料和传感反应过程中间体结构不明确、传感机制不清楚等缺点. 为应对这些挑战, 采用了全电子密度泛函理论探索铜掺杂氧化锌(标记为ZOC)及其复合物材料的结构和对NO₂的传感反应; 计算了复合物ZOC/CN和ZOC/Gr, 并与纯ZnO进行对比, 其中CN和Gr分别代表二维材料石墨型氮化碳和石墨烯. 计算显示, ZOC具有Cu-Zn杂核双金属活性吸附位点; 铜的引入增大了金属成分对最前线占据轨道贡献, 使得ZOC可同时通过Cu/Zn-O供体作用和反馈供体作用吸附NO₂; 其吸附自由能相比ZnO增大0.27 eV. 这很好地解释了铜掺杂氧化锌有更快NO₂响应时间的实验结果. 进一步复合CN能够提高NO₂传感性能: ZOC/CN具有最大的NO₂吸附能、很小的吸附第二个NO₂上坡能(决速步)和较大的硝酸盐生成能. 通过电子结构、反应能和界面相互作用计算, 揭示了传感NO₂的反应机制. 本工作为理解金属掺杂和材料复合等合成策略以及筛选有潜质敏感材料奠定了理论基础.

关键词: ZnO基敏感材料, 金属掺杂与二维材料复合, Cu-Zn双金属活性位点, 热力学反应与界面性质, 传感机制, 密度泛函理论计算

Of numerous environmental problems, the air pollution caused by toxic nitrogen dioxide has become more and more serious. Its timing detection is of utmost importance but challenging. It is known that NO₂ sensors fabricated by zinc oxide-derived materials suffer some issues. And thus synthetic strategies such as doping and combining have been developed to improve sensitive performance and modify operation condition. However, the relevant sensing reaction mechanism still remains unclear; moreover, the experimentally structural characterizations on sensitive materials (SMs) and reaction intermediates are rather difficult at the atomic level, which turn much worse for the doped and combined SMs. In the work, density functional theory calculations have been exploited to examine copper-doped zinc oxide (marked as ZOC) and its composites ZOC/CN and ZOC/Gr. CN and Gr are short for 2D materials, graphitic carbon nitride (g-C₃N₄) and graphene, respectively. The local structures have been accessible for these SMs and their intermediates along the reaction pathway. It is shown that ZOC bears the Cu-Zn heterobimetallic adsorption active sites, which hold NO₂ via Cu/Zn-O dative bonds. The introduction of copper increases metal contribution to high-lying occupied molecular orbitals (MOs). Major NO₂→ZOC donation and minor back-donation interactions have been recognized by charge decomposition analyses in terms of fragment MOs. Consequently, its adsorption free energy towards NO₂ is strengthened by 0.27 eV relative to pristine ZnO. These well interpret the experimental findings that the copper-doped zinc oxide has much faster response time. Further combination with g-C₃N₄enhances the NO₂-sensing performance, which turns out to be the best SM candidate. Exemplarily, ZOC/CN shows the most negative NO₂ adsorption energy (–0.31 eV), very small uphill energy for the rate-determining step (0.27 eV) and modest formation energy of nitrate (–1.06 eV). With these, the SM not only responses NO₂ rapidly but also desorbs nitrate at mild experimental condition. In brief, the theoretical study allows to deeply understand synthetic strategies that can improve sensing performance, and helps to search out novel sensitive materials.

Key words: ZnO-based sensitive material, metal-doping and 2D material combination, Cu-Zn heterobimetallic active sites, thermodynamics and interfacial property, sensing mechanism, DFT calculations

引用此文

王娟, 肖华敏, 谢丁, 郭元茹, 潘清江. 铜掺杂与氮化碳复合氧化锌材料结构和二氧化氮气体传感性质的密度泛函理论计算[J]. 化学学报, 2023, 81(11): 1493-1499.

Juan Wang, Huamin Xiao, Ding Xie, Yuanru Guo, Qingjiang Pan. Density Functional Theory Study of Structures of Copper-doped and Graphitic Carbon Nitride-combined Zinc Oxides and Their Boosted Nitrogen Dioxide-sensing Performance[J]. Acta Chimica Sinica, 2023, 81(11): 1493-1499.

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Parameters	ZOC-NO₂	ZOC/CN-NO₂	ZOC/Gr-NO₂	ZnO-NO₂ ^a	NO₂
O1—Cu	0.1988 (0.409)	0.1989 (0.405)	0.1983 (0.406)	—	—
O2—Zn	0.2256	0.2310	0.2267	0.2246	—
O1—N	0.1270 (1.405)	0.1275 (1.394)	0.1272 (1.402)	0.1208 (1.752)	0.1213 (1.750)
O2—N	0.1233 (1.561)	0.1231 (1.575)	0.1235 (1.560)	0.1239 (1.557)	0.1213 (1.750)
O1···O2	0.2208 (0.242)	0.2207 (0.242)	0.2207 (0.240)	0.2214 (0.340)	0.2228 (0.400)
O1—N—O2	123.8	123.3	123.3	129.7	133.4

Parameters	ZOC-NO₂	ZOC/CN-NO₂	ZOC/Gr-NO₂	ZnO-NO₂ ^a	NO₂
O1—Cu	0.1988 (0.409)	0.1989 (0.405)	0.1983 (0.406)	—	—
O2—Zn	0.2256	0.2310	0.2267	0.2246	—
O1—N	0.1270 (1.405)	0.1275 (1.394)	0.1272 (1.402)	0.1208 (1.752)	0.1213 (1.750)
O2—N	0.1233 (1.561)	0.1231 (1.575)	0.1235 (1.560)	0.1239 (1.557)	0.1213 (1.750)
O1···O2	0.2208 (0.242)	0.2207 (0.242)	0.2207 (0.240)	0.2214 (0.340)	0.2228 (0.400)
O1—N—O2	123.8	123.3	123.3	129.7	133.4

		ZnO		ZOC		ZOC/CN
Orbitals		LUMO	HOMO	LUMO	HOMO	LUMO+3	LUMO	HOMO
Energy/eV		–4.046	–6.384	–4.041	–6.155	–3.046	–3.717	–4.706
Contribution/%	O_Z	14.73	73.67	14.92	62.70	2.08	0.00	45.61
	Zn	79.44	7.81	73.50	4.10	58.07	0.00	0.00
	Cu	—	—	1.89	22.44	0.00	0.00	40.97
	CN	—	—	—	—	5.46	81.04	0.00
Composition/%		79.44 4s(Zn)	7.81 3d(Zn)	73.50 4s(Zn), 1.89 4s(Cu)	4.10 3d(Zn), 22.44 3d(Cu)	58.07 4s(Zn)	—	38.45 3d(Cu)
E_g/eV		2.338		2.114		0.989
∆_rG/eV		0.173		–0.101		–0.314

		ZnO		ZOC		ZOC/CN
Orbitals		LUMO	HOMO	LUMO	HOMO	LUMO+3	LUMO	HOMO
Energy/eV		–4.046	–6.384	–4.041	–6.155	–3.046	–3.717	–4.706
Contribution/%	O_Z	14.73	73.67	14.92	62.70	2.08	0.00	45.61
	Zn	79.44	7.81	73.50	4.10	58.07	0.00	0.00
	Cu	—	—	1.89	22.44	0.00	0.00	40.97
	CN	—	—	—	—	5.46	81.04	0.00
Composition/%		79.44 4s(Zn)	7.81 3d(Zn)	73.50 4s(Zn), 1.89 4s(Cu)	4.10 3d(Zn), 22.44 3d(Cu)	58.07 4s(Zn)	—	38.45 3d(Cu)
E_g/eV		2.338		2.114		0.989
∆_rG/eV		0.173		–0.101		–0.314

Complexes	BCPs ^a	ρ(r)	²ρ(r)	H(r)	ε	E_int/eV
ZnO-NO₂	Zn—O	0.0420	0.1774	–0.00244	0.0396	–0.670
ZOC-NO₂	Cu—O	0.0797	0.2802	–0.02526	0.0167	–1.641
	Zn—O	0.0421	0.1764	–0.00270	0.0432	–0.673
ZOC-2NO₂	Cu—O	0.0813	0.2547	–0.02706	0.0197	–1.603
	Zn—O	0.0472	0.1943	–0.00519	0.0354	–0.802
	O_Z—O	0.0156	0.0432	0.00009	0.0930	–0.144
ZOC-2NO₃	Cu—O	0.0735	0.2744	–0.02168	0.0301	–1.523
	Zn—O	0.0567	0.2302	–0.01116	0.0484	–1.087
	Zn—O	0.0538	0.2023	–0.00915	0.0357	–0.937
	Zn—O	0.0476	0.1970	–0.00598	0.0466	–0.833
ZOC/CN-NO₂	Cu—O	0.0811	0.3330	–0.02736	0.0535	–1.877
	Zn—O	0.0390	0.1532	–0.00164	0.0164	–0.566
ZOC/CN-2NO₂	Zn—O	0.0343	0.1465	–0.00052	0.0849	–0.512
	Cu—O	0.0800	0.2785	–0.02633	0.0322	–1.664
	O_Z—N ^b	0.0229	0.0756	0.00205	0.0380	–0.201
ZOC/CN-2NO₃	Cu—O	0.0759	0.2917	–0.02329	0.1063	–1.626
	Cu—O	0.0695	0.2510	–0.02099	0.0958	–1.425
	Zn—O	0.0530	0.2161	–0.00946	0.0640	–0.993
	Zn—O	0.0507	0.2015	–0.00758	0.0086	–0.891