Ag, Cu掺杂氧化石墨烯吸附NH<sub>3</sub>的第一性原理研究

万煜炜; 王瑞; 周文权; 王一平; 蔡亚楠; 王常

doi:10.7498/aps.74.20241737

摘要
基于第一性原理的密度泛函理论, 系统地研究了氧化石墨烯及其Ag与Cu掺杂对NH₃分子的吸附特性. 通过计算电荷分布、态密度、能带结构和吸附能, 研究了含氧基团及金属掺杂对氧化石墨烯气敏性能的调控效应. 通过对掺杂Ag原子的氧化石墨烯的态密度进行分析, 发现Ag原子与NH₃中的N原子的s, p和d轨道之间存在共振, 表明Ag原子和N原子之间形成了化学键. 这种化学键导致Ag对NH₃的吸附作用明显强于含氧基团, 从而使得掺杂后的氧化石墨烯的吸附能提升了数倍. 此外, Cu掺杂氧化石墨烯同样能够显著地提升其对NH₃的吸附性能. 在掺杂浓度均为3.13%的条件下, Cu掺杂的氧化石墨烯对NH₃表现出更强的吸附能力. 同时, Ag或Cu掺杂的氧化石墨烯中, 羧基和环氧基对NH₃的吸附模式由物理吸附转变为化学吸附; 而羟基则在掺杂前后始终显示出化学吸附特性. 综上所述, 金属掺杂的氧化石墨烯的吸附能会受到含氧基团和金属原子共同作用影响, 且Ag或Cu原子掺杂能显著提高氧化石墨烯对NH₃的吸附性能.

关键词:
掺杂 /

氧化石墨烯 /

第一性原理 /

吸附
Abstract
Graphene has attracted great attention due to its large specific surface area, high charge carrier mobility, and excellent electrical conductivity. However, the inherent structural integrity and zero bandgap characteristics of graphene limit its gas sensing properties. Consequently, researchers have embarked on exploring avenues such as doping graphene or using graphene oxide as a gas-sensitive material to design gas sensors that respond optimally to ammonia. This work, based on first-principle density functional theory, focuses on the field of ammonia gas sensors, investigating in detail the adsorption characteristics of ammonia molecules on graphene oxide (GO) and graphene oxide doped with Ag and Cu (AgGO, CuGO). By calculating parameters including charge distribution, density of states, band structures, and adsorption energy, this work delves into the influences of diverse oxygen-containing groups and metal doping on the gas sensing properties of graphene oxide. The research results show that there is a substantial charge density overlap between the density of states of hydroxyl groups in graphene oxide and NH₃ molecules, indicating a clear tendency towards chemical adsorption. It is particularly noteworthy that after NH₃ adsorption, the graphene oxide containing hydroxyl shows the highest charge transfer (0.078e) and adsorption energy (0.60 eV), which indicates that the adsorption efficacy of NH₃ is higher, followed by carboxyl groups and epoxy groups, which mainly participate in physical adsorption. Furthermore, this work delves into the influence of metal doping on graphene oxide, demonstrating that the adsorption capability of doped graphene oxide hinges upon the synergistic influence of oxygen-containing groups and metal atoms, with Ag-doped graphene oxide showing a several-fold increase in adsorption energy. Through the analysis of density of states, it is found that Ag atoms resonate with s, p, and d orbitals of the N atom in NH₃, proving the formation of a chemical bond between Ag atom and N atom. Moreover, a comparative analysis shows that Cu-doped graphene oxide (CuGO) has an increased charge transfer of about 0.020e and slightly higher adsorption energy than Ag-doped graphene oxide (AgGO) when adsorbing NH₃. Intriguingly, under the same doping concentration, CuGO exhibits superior adsorption performance to NH₃. It is worth noting that in graphene oxide doped with Ag or Cu, the adsorption mechanism of carboxyl and epoxy groups transforms from physical adsorption into chemical adsorption, while the hydroxyl groups maintain consistent chemical adsorption properties before and after doping. This indicates that doping with Ag or Cu atoms can significantly enhance the adsorption capability of graphene oxide to NH₃.

Keywords:
doping /

graphene oxide /

first principle /

adsorption
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图 1 优化前相关建模图　(a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃; (e) AgGO-O-NH₃; (f) AgGO-OH-NH₃; (g) AgGO-COOH-NH₃; (h) CuGO-O-NH₃; (i) CuGO-OH-NH₃; (j) CuGO-COOH-NH₃

Fig. 1. Related model diagrams before optimization: (a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃; (e) AgGO-O-NH₃; (f) AgGO-OH-NH₃; (g) AgGO-COOH-NH₃; (h) CuGO-O-NH₃; (i) CuGO-OH-NH₃; (j) CuGO-COOH-NH₃.

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图 2 优化后G和含有不同含氧基团的GO吸附NH₃的俯视图和侧视图　(a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃

Fig. 2. Top and side views of optimized G and GO with different oxygen-containing groups adsorbing NH₃: (a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃.

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图 3 G和含有不同含氧基团的GO吸附NH₃的电荷总密度图(等值面为0.2)　(a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃

Fig. 3. Total charge density of G and GO with different oxygen-containing groups adsorbing NH₃ (The isosurface value is 0.2): (a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃.

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图 4 G和含有不同含氧基团的GO吸附NH₃的差分电荷密度图(等值面为0.05)　(a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃

Fig. 4. Charge density difference of G and GO with different oxygen-containing groups adsorbing NH₃ (The isosurface value is 0.05): (a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃.

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图 5 G和GO的能带结构　(a) G; (b) GO-O; (c) GO-OH; (d) GO-COOH

Fig. 5. Band structures of G and GO: (a) G; (b) GO-O; (c) GO-OH; (d) GO-COOH.

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图 6 G和GO吸附NH₃的态密度图　(a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃

Fig. 6. Density of states of G and GO adsorbing NH₃: (a) G-NH₃; (b) GO-O-NH₃; (c) GO-OH-NH₃; (d) GO-COOH-NH₃.

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图 7 优化后含不同含氧基团的AgGO和GO吸附NH₃的俯视图　(a) GO-O-NH₃; (b) GO-OH-NH₃; (c) GO-COOH-NH₃; (d) AgGO-O-NH₃; (e) AgGO-OH-NH₃; (f) AgGO-COOH-NH₃

Fig. 7. Top views of optimized AgGO and GO with different oxygen-containing groups adsorbing NH₃: (a) GO-O-NH₃; (b) GO-OH-NH₃; (c) GO-COOH-NH₃; (d) AgGO-O-NH₃; (e) AgGO-OH-NH₃; (f) AgGO-COOH-NH₃.

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图 8 GO与AgGO的DOS和PDOS　(a) GO-O-NH₃和AgGO-O-NH₃的DOS; (b) GO-OH-NH₃和AgGO-OH-NH₃的DOS; (c) GO-COOH-NH₃和AgGO-COOH-NH₃的DOS; (d) AgGO-O-NH₃中Ag的DOS和PDOS; (e) AgGO-OH-NH₃中Ag的DOS和PDOS; (f) AgGO-COOH-NH₃中Ag的DOS和PDOS; (g) AgGO-O-NH₃中N的DOS和PDOS; (h) AgGO-OH-NH₃中N的DOS和PDOS; (i) AgGO-COOH-NH₃中N的DOS和PDOS

Fig. 8. DOS and PDOS of GO and AgGO: (a) DOS of GO-O-NH₃ and AgGO-O-NH₃; (b) DOS of GO-OH-NH₃ and AgGO-OH-NH₃; (c) DOS of GO-COOH-NH₃ and AgGO-COOH-NH₃; (d) DOS and PDOS of Ag in AgGO-O-NH₃; (e) DOS and PDOS of Ag in AgGO-OH-NH₃; (f) DOS and PDOS of Ag in AgGO-COOH-NH₃; (g) DOS and PDOS of N in AgGO-O-NH₃; (h) DOS and PDOS of N in AgGO-OH-NH₃; (i) DOS and PDOS of N in AgGO-COOH-NH₃.

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图 9 含有不同含氧基团的AgGO和CuGO吸附NH₃的电荷总密度图(等值面为0.2)　(a) AgGO-O-NH₃; (b)AgGO-OH-NH₃; (c) AgGO-COOH-NH₃; (d) CuGO-O-NH₃; (e) CuGO-OH-NH₃; (f) CuGO-COOH-NH₃.

Fig. 9. Total charge density of AgGO and GO with different oxygen-containing groups adsorbing NH₃ (The isosurface value is 0.2): (a) AgGO-O-NH₃; (b) AgGO-OH-NH₃; (c) AgGO-COOH-NH₃; (d) CuGO-O-NH₃; (e) CuGO-OH-NH₃; (f) CuGO-COOH-NH₃.

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图 10 AgGO和CuGO的能带结构　(a) AgGO-O; (b) AgGO-OH; (c) AgGO-COOH; (d) CuGO-O; (e) CuGO-OH; (f) CuGO-COOH

Fig. 10. Band structures of AgGO and CuGO: (a) AgGO-O; (b) AgGO-OH; (c) AgGO-COOH; (d) CuGO-O; (e) CuGO-OH; (f) CuGO-COOH.

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图 11 AgGO与CuGO的DOS　(a) AgGO-O-NH₃中Ag和NH₃的DOS; (b) AgGO-OH-NH₃中Ag和NH₃的DOS; (c) AgGO-COOH-NH₃中Ag和NH₃的DOS; (d) CuGO-O-NH₃中Cu和NH₃的DOS; (e) CuGO-OH-NH₃中Cu和NH₃的DOS; (f) CuGO-COOH-NH₃中Cu和NH₃的DOS

Fig. 11. DOS of AgGO and CuGO: (a) DOS of Ag and NH₃ in AgGO-O-NH₃; (b) DOS of Ag and NH₃ in AgGO-OH-NH₃; (c) DOS of Ag and NH₃ in AgGO-COOH-NH₃; (d) DOS of Cu and NH₃ in CuGO-O-NH₃; (e) DOS of Cu and NH₃ in CuGO-OH-NH₃; (f) DOS of Cu and NH₃ in CuGO-COOH-NH₃.

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表 1 G和含有不同含氧基团的GO吸附NH₃的几何参数. C1, C2和C3为与含氧基团相连的最近的三个碳原子; D表示吸附距离

Table 1. Structural parameters of G and GO with different oxygen-containing groups adsorbing NH₃: C1, C2, and C3 are the three nearest carbon atoms connected to the oxygen-containing group; D represents the adsorption distance.

Species	Bond angles/(°)			D/Å
Species	C1-C2	C2-C3	C3-C1	D/Å
G-NH₃	120.06	119.98	119.94	3.24 (N—C)
GO-O-NH₃	118.75	118.19	118.17	2.28 (H—O)
GO-OH-NH₃	112.95	112.72	112.77	1.80 (N—H)
GO-COOH-NH₃	119.57	—	—	2.44 (H—O)

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表 2 G和含有不同含氧基团的GO吸附NH₃的吸附能和电荷布居

Table 2. Adsorption energy and Mulliken charge of G and GO with different oxygen-containing groups adsorbing NH₃.

System	Mulliken charge/e				E_{ads /}eV
System	C1	C2	C3	NH₃	E_{ads /}eV
G-NH₃	0.013	0.004	–0.039	0.022	–0.15
GO-O-NH₃	0.112	0.024	0.026	0.005	–0.11
GO-OH-NH₃	0.004	–0.035	0.006	0.078	–0.60
GO-COOH-NH₃	0.125	–0.016	—	0.036	–0.17

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表 3 带有不同含氧基团的AgGO和GO吸附NH₃的吸附距离D、电荷转移Q和吸附能E_ads

Table 3. Adsorption distance D, charge transfer Q, and adsorption energy E_ads of AgGO and GO with different oxygen-containing groups adsorbing NH₃.

Species	D/Å	Q/e		E_ads/eV
Species	D/Å	NH₃	Ag	E_ads/eV
GO-O-NH₃	2.28 (H-O)	0.005	—	–0.11
AgGO-O-NH₃	2.29 (N-Ag)	0.171	–0.038	–1.25
GO-OH-NH₃	1.80 (N-H)	0.078	—	–0.60
AgGO-OH-NH₃	2.29 (N-Ag)	0.160	–0.033	–1.26
GO-COOH-NH₃	2.44 (H-O)	0.036	—	–0.17
AgGO-COOH-NH₃	2.29 (N-Ag)	0.170	–0.082	–1.39

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表 4 带有不同含氧基团AgGO和CuGO吸附NH₃的电荷转移Q和吸附能E_ads

Table 4. Charge transfer Q and adsorption energy E_ads of AgGO and GO with different oxygen-containing groups adsorbing NH₃.

Species	Q /e		E_ads/eV
Species	NH₃	Ag/Cu	E_ads/eV
AgGO-O-NH₃	0.171	–0.038	–1.25
CuGO-O-NH₃	0.192	0.020	–1.39
AgGO-OH-NH₃	0.160	–0.033	–1.26
CuGO-OH-NH₃	0.180	–0.001	–1.43
AgGO-COOH-NH₃	0.170	–0.082	–1.39
CuGO-COOH-NH₃	0.192	0.034	–1.34

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Ag, Cu掺杂氧化石墨烯吸附NH₃的第一性原理研究

First-principles study of NH₃ adsorption on Ag- and Cu doped graphene oxide

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Ag, Cu掺杂氧化石墨烯吸附NH3的第一性原理研究

First-principles study of NH3 adsorption on Ag- and Cu doped graphene oxide

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Ag, Cu掺杂氧化石墨烯吸附NH₃的第一性原理研究

First-principles study of NH₃ adsorption on Ag- and Cu doped graphene oxide