A theoretical study of H2S adsorption and dissociation mechanism on defected graphene doped with Pt
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摘要: 通过第一性原理计算研究了四种Pt或Pt团簇修饰石墨烯材料的几何结构、电子结构及其对硫化氢(H2S)分子吸附、分解行为。结果表明，H2S在四种材料上均为弱的物理吸附，但H2S分解后的HS和S可以稳定吸附在材料表面。对于H2S的分解过程，考虑了三个基本过程：(I) H2S (g)→H2S (ads)；(II) H2S (ads)→HS (ads) + H (ads)；(III) HS (ads)→H (ads) + S (ads)。H2S在四种不同表面的第一H–S键断裂能垒分别为1.69、0.52、0.01和0.24 eV；H–S中断裂第二H–S键的能垒分别为2.34、1.08、0.81和1.12 eV。因此，H2S完全解离的控制步骤是第二个H–S键断裂过程。结合H2S吸附和分解结果，研究发现单Pt原子掺杂缺陷石墨烯有利于吸附H2S，但对解离不利；Pt团簇掺杂的空位较大的缺陷石墨烯能够轻松吸附并消除H2S分子，有望成为吸附、分解H2S气体的理想材料。Abstract: The adsorption and dissociation of hydrogen sulfide (H2S) molecule have been discussed on Pt or Pt cluster including 4 Pt atoms (Pt4) doped graphene with different vacancy (VG) by Density Functional Theory (DFT). The results presented including adsorption energies, structural and electronic properties and workfunction. It has found that H2S and H atom are weakly adsorbed on Pt/Pt4-VG, while HS and S atom are strongly chemisorbed on different surfaces. By using climbing nudged elastic band method (CI–NEB), three elementary processes have been considered: (ⅰ) H2S(gas)→H2S(ads); (ⅱ) H2S(ads)→HS(ads) + H(ads); (ⅲ) HS(ads)→H(ads) + S(ads). The energy barrier to break the first H–S bond in H2S on four different surfaces are 1.69, 0.52, 0.01 and 0.24 eV respectively. In contrast, the energy barrier to break the second H–S bond in HS are 2.34, 1.08, 0.81 and 1.12 eV respectively. It is suggested that the control step of the complete dissociation of H2S is the second H–S bond rupture process. The trend of predicted results within this study reveal that single Pt atom doped defected graphene is good for adsorption of H2S, but to the disadvantage of dissociation. Pt cluster doped defected graphene with bigger vacancy could succeed in adsorbing and eliminating H2S molecule easily; this work unveils definitive theoretical procedures which can be tested and validated experimentally.
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Key words:
- DFT /
- defected graphene /
- Pt doped /
- Hydrogen sulfide
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图 1 MVG (a)和DVG (b)的局域结构单Pt原子掺杂MVG (c)和DVG (d)，Pt团簇掺杂MVG (e)和DVG (f) (棕色和蓝色原子分别代表C和Pt)
Figure 1 Local structures of MVG (a) and DVG (b) Single Pt atoms doped with MVG (c) and DVG (d), Pt clusters doped with MVG (e) and DVG (f), and brown and blue atoms represent C and Pt, respectively
图 2 不同表面Pt原子相邻的C的投影态密度(PDOS) (a和b)和电荷差异(c−f) 。费米能级和等值面分别设为0 eV和0.005 eV/Å3。电荷积累呈蓝色，电荷减少呈黄色，原子的颜色编码与图1相同。Δq代表总电荷。负意味着电子从Pt / Pt4转移到C
Figure 2 Projected Density of States (PDOS) (a and b) and charge differences for C adjacent to Pt atom in different surfaces (c−f). The Fermi level and isosurfaces are respectively set to 0 eV and 0.005 eV/Å3. Charge accumulation is in blue and depletion in yellow and the color coding of atoms are the same as Figure 1. Δq stands for the total charge. Negative means electrons are transferred from Pt/Pt4 to C.
图 3 Pt掺杂缺陷石墨烯上吸附H2S的优化几何构型：(a) H2S / Pt-MVG；(b) H2S / Pt-DVG；(c) H2S / Pt4 - MVG；(D) H2S / Pt4 - DVG。
Figure 3 Optimized geometries for H2S adsorbed on Pt doped defected grapheme: (a) H2S/Pt-MVG; (b) H2S/Pt-DVG; (c) H2S/Pt4-MVG; (d) H2S/Pt4-DVG. The yellow and red atoms represent S and H respectively. all lengths are given in Å.
图 4 不同结构的功函数
Figure 4 Work functions of different structures: (a) Pt-MVG; (b) Pt-DVG; (c) Pt4- MVG; (D) Pt4- DVG
图 5 吸附在Pt掺杂缺陷石墨烯上的HS的优化几何构型(a) HS / Pt-MVG；(b) HS/ Pt-DVG；(c) HS / Pt4 - MVG；(D) HS / Pt4 - DVG
Figure 5 Optimized geometries for HS adsorbed on Pt doped defected grapheme: (a) HS/Pt-MVG; (b) HS/Pt-DVG; (c) HS/Pt4-MVG; (d) HS/Pt4-DVG.
图 6 不同表面Pt原子d带中心与HS吸附能的关系
Figure 6 Relationship between the d-band center of the different surface Pt atoms and the HS adsorption energy
图 7 HS在不同表面吸附的PDOS。费米能级设为零(插图是不同结构的电子局域函数)
Figure 7 Relationship between the d-band center of the different surface Pt atoms and the HS adsorption energy
图 8 AIMD计算得到的不同Pt掺杂缺陷石墨烯中选择性Pt–S和Pt–H键长的演化
Figure 8 Evolution of selective Pt-S and Pt-H bond length in different Pt doped defected graphene derived from AIMD calculations.
图 9 计算得到的MEPs在不同表面上解离H2S的相对能量
Figure 9 Relative energies of calculated MEPs for the dissociation of H2S on the different surfaces
图 10 H2S解离过程中不同状态的结构
Figure 10 H2S Structure of different states during dissociation (length in A in figure)
表 1 MVG / DVG上Pt / Pt4掺杂的计算
Table 1 Summary of the calculated results for Pt/Pt4 doped on MVG/DVG
Pt-MVG Pt-DVG Pt4-MVG Pt4-DVG ΔEb/eV −4.57 −4.43 −7.56 −7.01 $ {\overline d _{{\rm{P}}{\rm{t}} - C}} $/Å 1.93 1.98 1.96 2.05 dPt–Pt min/Å − − 2.55 2.49 dPt–Pt, max/Å − − 2.62 2.60 $\angle $C–Pt–C/° 90.28 88.14 87.82 85.90 
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表 2 H2S和HS在Pt / Pt4掺杂石墨烯表面的吸附能( ΔEads )和电荷转移(ΔqM)
Table 2 Adsorption energy (Eads) and charge transfer (ΔqM) of H2S and HS adsorbed on Pt/Pt4 doped graphene surface
Pt-MVG Pt-DVG Pt4-MVG Pt4-DVG ΔEads/ eV H2S −0.85 −0.27 −1.81 −2.30 HS −3.24 −3.23 −4.35 −3.96 ΔqM/e H2S −0.13 −0.013 −0.17 −0.21 HS 0.26 0.14 0.18 0.12
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