双金属MOF衍生的Ru掺杂Cu基电催化材料在碱性介质中的高效析氢​

武汉大学高等研究院阴国印教授课题组和湖北工程学院生物医学材料工业技术研究所朱磊教授课题组合作报道了镍/铜双金属协同催化的非活化末端烯烃的1,n-芳硅化反应(n=2-5),以题为“Synergistic Ni/Cu catalyzed migratoryarylsilylation of terminal olefins”在线发表于Science Bulletin。钾离

合理设计和制备廉价且高效的电催化析氢（HER）材料对电解水有着十分重要的意义。本文开发了一种通过热解基于Ru离子交换方法得到的双金属Ru-Cu-BTC金属有机骨架简易制备Ru掺杂Cu负载的多孔碳材料（Ru-Cu@C）的方法。该催化剂在碱性电解液中表现出了优异的HER性能，电流密度为10 mA/cm²时的过电位低至20 mV，且Tafel斜率仅有37 mV/dec, 该性能甚至超越了商用Pt/C催化剂。同时，密度泛函理论计算（DFT）结果表明，在Cu纳米晶的晶格中引入Ru原子后，H₂的吸附能接近于零，这极大的促进了H₂在催化剂表面的脱附，显著改善了HER性能。该策略为开发廉价高效的碱性HER电催化剂提供了新的思路。

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图文速览

Fig. 1. Schematic illustration of the synthesis process for the Ru-Cu@C electrocatalysts.

Fig. 2. SEM and TEM images of Ru-Cu@C-2. (a) SEM, (b) TEM, (c) STEM (size histogram images), (d) HRTEM imageof Ru-Cu@C-2, (e-h) HAADF-STEM images and corresponding EDX maps of Ru-Cu@C-2.

Fig. 3.  Structural andcompositional analyses of Ru-Cu@C-n. (a) XRD patterns of Ru-Cu@C-1, Ru-Cu@C-2 and Ru-Cu@C-3. (b) N₂ adsorption-desorption isotherm of Ru-Cu@C-2 at 77 K (inset: pore sizedistribution). (c, d) The XPS spectrum of Ru-Cu@C-2: Cu 3p spectra and Ru 3d + C 1s spectra.

Fig. 4. HER performance in 1 mol/L  KOH solution. (a, b) HER polarization curvesand the Tafel plots of Ru-Cu@C-1, Ru-Cu@C-2, Ru-Cu@C-3 and Pt/C 20% with thesame mass loading. (c, d) HER polarization curves and the Tafel plots ofRu-Cu@C-2, Cu@C and Ru@C with the same mass loading. The abbreviation E represents potential and J represents current density.

Fig. 5.  The adsorption sites of H atoms onoptimized (a−c) pure and (d−f) Ru-doped surfaces. The suitable adsorption sites are marked byblue lines, and numbers. Corresponding Gibbs free energy values are listed in Table S5 (online). The numbers indicate different sites composed of Cu only as thecorresponding pure surfaces, while the black “3” in (e) indicates an unstableadsorption site. The surface atoms are displayed by ball and stick model, whileother atoms are displayed by line model. The orange spheres, dark green spheresand white spheres denote Cu atoms, Ru atoms and H atoms, respectively. (g) The comparison of ΔG_H values between the Ru-doped Cu surfaces and the previously reported highly active HER electrocatalysts.

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Mengya Yang, Long Jiao, Huilong Dong, Liujiang Zhou, Changqing Teng,  Dongming Yan, Tian-Nan Ye, Xiaoxin Chen, Yi Liu*, Hai-Long Jiang*. Conversion of bimetallic MOF to Ru-doped Cuelectrocatalysts for efficient hydrogen evolution in alkaline media. ScienceBulletin, 2021, 66(3): 257-264

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