Density Functional Theory Study of Structures of Copper-doped and Graphitic Carbon Nitride-combined Zinc Oxides and Their Boosted Nitrogen Dioxide-sensing Performance

doi:10.6023/A23060312

Abstract

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

Cite this article

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

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