Porous carbon supported ruthenium single atom and ruthenium nanoclusters catalysts for efficient hydrogen evolution reaction
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摘要: 高效析氢反应(HER)电催化剂的制备对氢能的大规模推广具有重大的意义。本文以羧甲基纤维素钠(CMC-Na)和RuCl3为原料,利用Ru离子与CMC-Na在溶液中配位制备了Ru-CMC-Na水凝胶,随后通过冷冻干燥、高温退火和酸洗制备了多孔碳负载Ru单原子和Ru纳米团簇的催化剂RuSA+NC/C-2。催化剂RuSA+NC/C-2在酸性和碱性电解质中都具有优异的HER活性和稳定性,达到10 mA·cm−2电流密度,所需过电位分别20 mV和23 mV,经过12 h的恒电位测试其活性未见明显衰减。催化剂RuSA+NC/C-2中Ru的含量为5.52wt%,在1 mol/L KOH电解质中,过电位为0.05 V时,催化剂的质量活性是商业Pt/C的5.8倍。通过对催化剂RuSA+NC/C-2的物理表征测试发现,催化剂RuSA+NC/C-2的多孔结构和大比表面积,可以暴露更多的活性位点。Ru单原子与Ru纳米团簇结构提高了Ru原子的利用率。通过XPS分析,Ru与碳载体间存在强相互作用,形成了缺电子态的Ru,从而提高了催化剂的HER活性。Abstract: The preparation of electrocatalyst for high efficiency hydrogen evolution reaction (HER) is of great significance to the large-scale promotion of hydrogen energy. In this paper, using sodium carboxymethyl cellulose (CMC-NA) and RuCl3 as raw materials, Ru-CMC-Na hydrogel was prepared by the coordination of Ru ions with CMC-Na in solution. Then, porous carbon supported Ru single atom and Ru nanocluster catalyst RuSA+NC/C-2 was prepared by freeze-drying, high temperature annealing and pickling. The catalyst RuSA+NC/C-2 shows excellent HER activity and stability in both acidic and alkaline electrolytes, reaching 10 mA·cm−2 current density at 20 mV and 23 mV, respectively. After 12 h chronoamperometry test, the activity of RuSA+NC/C-2 shows no obvious attenuation. The mass activity of RuSA+NC/C-2 is 5.8 times that of commercial Pt/C when the overpotential is 0.05 V in 1 mol/L KOH electrolyte. The physical characterization of RuSA+NC/C-2 catalyst shows that the porous structure and large specific surface area of RuSA+NC/C-2 catalyst can expose more active sites. Ru single atom and Ru nanocluster structure improve the utilization rate of Ru atom. XPS analysis shows that there is a strong interaction between Ru and carbon support, resulting in the formation of electron-deficient Ru, thus improving HER activity of the catalyst.
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图 2 催化剂RuSA+NC/C-2的物理表征:(a) XRD图像;((b)~(d)) 高角度环形场暗场扫描透射电镜(HAADF-STEM)图像;((e)、(f)) 高分辨透射电镜图像;(g) HAADF-STEM图像及其对应的原子分辨率EDS元素扫描图像
Figure 2. Characterization of RuSA+NC/C-2: (a) XRD pattern; ((b)-(d)) High angle annular dark field image (HAADF)-scanning transmission electron microscope (STEM) images; ((e), (f)) HRTEM images; (g) HAADF-STEM image and corresponding atomic-resolution EDS mapping images
图 4 (a) RuSA+NC/C-2的拉曼图谱;(b) RuSA+NC/C-2的氮气吸脱附和孔径分布图;(c) RuSA+NC/C-2和商业Ru/C的Ru3p高分辨光电子能谱;(d) RuSA+NC/C-2的C1s+Ru3d高分辨光电子能谱
Figure 4. (a) Raman spectrum of RuSA+NC/C-2; (b) N2 adsorption/desorption isotherms and pore size distributions for RuSA+NC/C-2; (c) XPS spectra of Ru3p for RuSA+NC/C-2 and commercial Ru/C; (d) XPS spectrum of C1s+Ru3d for RuSA+NC/C-2
ID/IG—Intensity ration of D and G band ratio; STP—Standard state: 273.15 K, 100 kPa; SSA—Specific surface area; V—Pore volume; D—Pore diameter
图 6 催化剂RuSA+NC/C-2和对比样品在1 mol/L KOH溶液中的析氢反应(HER)性能:(a) 线性伏安曲线;(b)质量活性;(c) 塔菲尔斜率;(d) 双电层电容值;(e) RuSA+NC/C-2在经过5000圈循环伏安测试前后的线性伏安曲线对比;(f) RuSA+NC/C-2的恒电位稳定性测试
Figure 6. Hydrogen evolution reaction (HER) performance of RuSA+NC/C-2 and contrast samples in 1 mol/L KOH: (a) LSV curves; (b) Mass activities; (c) Tafel slopes; (d) Electric double-layer capacitances Cdl; (e) Polarization curves recorded before and after 5000 potential cycles of RuSA+NC/C-2; (f) Chronoamperometric curve of RuSA+NC/C-2
Janodic−Jcathodic—Anodic current density minus the cathodic current density at 0.15 V in the cyclic voltammetry curve; M—Noble metal; RHE—Reversible hydrogen electrode
图 7 催化剂Carbon (a)、RuSA/C (b)、RuSA+NC/C-1 (c)、RuSA+NC/C-2 (d)、RuSA+NC/C-3 (d)和商业Ru/C (f)在1 mol/L KOH电解质中0.1~0.2 V vs RHE电位区间不同扫速的循环伏安曲线
Figure 7. CV curves recorded at different scan rates for Carbon (a), RuSA/C (b), RuSA+NC/C-1 (c), RuSA+NC/C-2 (d), RuSA+NC/C-3 (d) and commercial Ru/C (f) in a non-Faradaic potential window from 0.1-0.2 V vs RHE in 1 mol/L KOH
图 9 催化剂RuSA+NC/C-2和对比样品在0.5 mol/L H2SO4溶液中的HER性能:(a) 线性伏安曲线;(b) 质量活性;(c) 塔菲尔斜率;(d) 双电层电容值;(e) 催化剂RuSA+NC/C-2在经过5000圈循环伏安测试前后的线性伏安曲线对比;(f) 催化剂RuSA+NC/C-2的恒电位稳定性测试
Figure 9. HER performance of RuSA+NC/C-2 and contrast samples in 0.5 mol/L H2SO4: (a) LSV curves; (b) Mass activities; (c) Tafel slopes; (d) Cdl of RuSA+NC/C-2 and compared samples; (e) Polarization curves recorded before and after 5000 potential cycles of RuSA+NC/C-2; (f) Chronoamperometric curve of RuSA+NC/C-2
图 10 催化剂Carbon (a)、RuSA/C (b)、RuSA+NC/C-1 (c)、RuSA+NC/C-2 (d)、RuSA+NC/C-3 (e)和商业Ru/C (f)在0.5 mol/L H2SO4电解质中0.1~0.2 V vs RHE电位区间不同扫速的循环伏安曲线
Figure 10. CV curves recorded at different scan rates for Carbon (a), RuSA/C (b), RuSA+NC/C-1(c), RuSA+NC/C-2 (d), RuSA+NC/C-3 (e) and commercial Ru/C (f) in a non-Faradaic potential window from 0.1-0.2 V vs RHE in 0.5 mol/L H2SO4
图 11 不同退火温度制备的催化剂RuSA+NC/C-2-X在1 mol/L KOH中的线性伏安曲线(a)和双电层电容(b);催化剂RuSA+NC/C-2-600 (c)和RuSA+NC/C-2-800 (d)在非法拉第区间0.1~0.2 V vs RHE不同扫速下的循环伏安曲线
Figure 11. LSV curves (a) and Cdl (b) of RuSA+NC/C-2-X in 1 mol/L KOH; CV curves recorded at different scan rates for RuSA+NC/C-2-600 (c) and RuSA+NC/C-2-800 (d) in a non-Faradaic potential window from 0.1-0.2 V vs RHE in 1 mol/L KOH
图 12 不同温度下退火制备的催化剂RuSA+NC/C-2-X在0.5 mol/L H2SO4电解质中的线性伏安曲线(a)和双电层电容(b);催化剂RuSA+NC/C-2-600 (c)和RuSA+NC/C-2-800 (d)在非法拉第区间0.1~0.2 V vs RHE不同扫速下的循环伏安曲线
Figure 12. LSV curves (a) and Cdl (b) of RuSA+NC/C-2-X in 0.5 mol/L H2SO4; CV curves recorded at different scan rates for RuSA+NC/C-2-600 (c) and RuSA+NC/C-2-800 (d) in a non-Faradaic potential window from 0.1-0.2 V vs RHE in 0.5 mol/L H2SO4
表 1 不同催化剂的制备条件
Table 1. Preparation conditions of different catalysts
Sample RuCl3·xH2O/mg Annealing temperature/℃ Carbon 0 700 RuSA/C 20 700 RuSA+NC/C-1 50 700 RuSA+NC/C-2 100 700 RuSA+NC/C-3 150 700 RuSA+NC/C-2-600 100 600 RuSA+NC/C-2-800 100 800 -
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