Preparation of N-doped MoP-based core-shell nanorods and their electrocatalytic performance in hydrogen evolution
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摘要: 通过气-固反应方式对三氧化钼-乙二胺有机无机杂化材料(MoO3/EDA)进行原位磷化,利用空间限域效应合成了N掺杂的MoP基核壳纳米棒(N-MoP/NC-8)电化学析氢催化剂。表征结果显示,N-MoP/NC-8由N掺杂碳层包覆的N掺杂钼(MoP)组成,引入的电负性原子调节了活性相电子结构,同时碳层与MoP之间的复合限制了MoP内部团聚,产生较大的孔体积和比表面积,在双重调控下N-MoP/NC-8催化剂表现出较好的析氢性能(在0.5 mol/L H2SO4溶液中,10 mA/cm2电流密度下的过电位为92 mV,Tafel斜率为68 mV/dec),且稳定性超过20 h。Abstract: N-doped MoP-based core-shell nanorods (N-MoP/NC-8) were synthesized by in-situ phosphorization of molybdenum trioxide-ethylenediamine organic-inorganic hybrid material (MoO3/EDA) via a gas-solid reaction; their electrocatalytic performance in hydrogen evolution was investigated. The results indicate that N-MoP/NC-8 is composed of N-doped molybdenum phosphide (MoP) coated by N-doped carbon layer. The introduced electronegative atom can regulate the electronic structure of the active phase, whilst the combination of carbon layer and MoP can inhibit the internal agglomeration of MoP, resulting in large pore volume and surface area. Owing to such a dual effect, the N-MoP/NC-8 catalyst shows excellent performance in electrocatalytic hydrogen evolution and great charge transfer ability; the overpotential is 92 mV at 10 mA/cm2 current density in 0.5 mol/L H2SO4 solution, with a Tafel slope of 68 mV/dec and a durability of above 20 h.
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Key words:
- confined space /
- doping /
- ethylenediamine /
- molybdenum phosphide /
- hydrogen evolution reaction
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图 3 ((a)、(b)) MoO3,(c) MoO3/EDA,(d) N-MoP/NC-7,(e) N-MoP/NC-8,(f) N-MoP/NC-9,(g) N-MoP/NC-750,(h) N-MoP/NC-850和 (i) MoP-8的SEM照片;(j) MoP -8和 (k) N-MoP/NC-8的TEM照片;(l) N-MoP/NC-8的高分辨TEM照片;(m) N-MoP/NC-8的元素EDX mapping分布;N-MoP/NC-8和MoP-8的 (n) N2吸附-脱附曲线和 (o) 孔径分布
Figure 3 SEM images of ((a), (b)) MoO3, (c) MoO3/EDA, (d) N-MoP/NC-7, (e) N-MoP/NC-8, (f) N-MoP/NC-9, (g) N-MoP/NC-750, (h) N-MoP/NC-850 and (i) MoP-8; TEM images of (j) N-MoP/NC-8 and (k) MoP-8; HRTEM image of N-MoP/NC-8 (l); Elements EDX mapping of N-MoP/NC-8 (m); N2 adsorption desorption plots (n) and pore size distribution (o) of N-MoP/NC-8 and MoP-8
图 9 (a) N-MoP/NC-8和MoP-8的1000圈CV循环前后的LSV极化曲线和计时电位(CP)曲线;((b)、(c)) N-MoP/NC-8和((d)、(e)) MoP-8在CP测试前后的TEM照片;(f) N-MoP/NC-8和 (g) MoP-8在CP测试后的Mo、P元素的XPS光谱谱图
Figure 9 LSV polarization curves (a) before and after 1000 cycles of CV and time-dependent potential (CP) curves of N-MoP/NC-8 and MoP-8; TEM images of N-MoP/NC-8 ((b), (c)) and MoP-8 ((d), (e)) before and after CP; Mo and P XPS spectra of (f) N-MoP/NC-8 and (g) MoP-8 after CP
表 1 N-MoP/NC-8和MoP-8的比表面积、孔体积和平均孔径
Table 1 Surface area, pore volume and average pore diameter of N-MoP/NC-8 and MoP-8
Catalyst Surface area/(m2·g−1) Pore volume/(cm3·g−1) Pore diameter/nm N-MoP/NC-8 117.30 0.186 7.9 MoP-8 60.24 0.064 5.5 表 2 N-MoP/NC-8和MoP-8的D峰和G峰
Table 2 D-peak and G-peak of N-MoP/NC-8 and MoP-8
Catalyst D/cm−1 G/cm−1 ID/IG N-MoP/NC-8 1358 1584 ≈0.9 MoP-8 − − − 表 3 N-MoP/NC-8和MoP-8的Mo、P组分含量以及结合能差值的XPS光谱数据
Table 3 Data derived from XPS spectra of N-MoP/NC-8 and MoP-8
Catalyst Binding energy/eV Elements of catalyst Moδ+ 3d5/2 Moδ+ 3d3/2 Pδ+ 3d3/2 Pδ+ 3d1/2 Mo/% P/% N-MoP/NC-8 228.6 231.7 129.8 130.6 10.49 15.18 MoP-8 228.2 231.4 129.6 130.4 12.19 10.17 Difference 0.4 0.3 0.2 0.2 − − 表 4 不同合成条件的MoP和Pt/C的电化学性能
Table 4 Electrochemical performance of the MoP materials obtained under different synthesis conditions
Catalyst η10/mV Tafel slope/
(mV·dec−1)Impedance/
ΩCdl/
(mF·cm−2)N-MoP/NC-8 92 68 2 26 N-MoP/NC-7 112 71 2.4 18 N-MoP/NC-9 111 86 2.6 19 N-MoP/NC-750 127 77 2.5 12 N-MoP/NC-850 128 72 2.5 12 MoP-8 226 115 4 4 Pt/C 31 37 1 — 表 5 不同MoP基复合材料的电化学性能
Table 5 Electrochemical performance of different MoP-based composites
Catalyst η10/mV Tafel slope/(mV·dec−1) Impedance/Ω Ref. N-MoP/NC-8 92 68 2 this work MoP-8 226 115 4 this work MoP/MoS2/MoO2 135 67 ~150 [11] MoP 200 66 ~15 [39] MoP/NC 183 57 ~10 [39] MoP/Co2P/CFP 140 80 13 [43] MoP 120 52 − [44] S-MoP 91 − − [44] NiMoP/C 158 111 5 [45] MoP/NPG 148 49 13 [46] MoP/NCNT-NGR 100 44 10 [47] N/C/MoP 169 51 − [48] MoP@NPSC 71 75 2 [49] Mo2C-MoP NPC/CFP-800 85 66 − [50] MoP NA/CC 124 58 66 [51] MoP/N, P-CNTs 116 − − [52] -
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