Cactus-like NC/CoxP electrode enables efficient and stable hydrogen evolution for saline water splitting
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摘要: 设计高效、稳定的析氢催化剂是盐水电解技术发展的必然要求。本文通过原位生长策略在泡沫镍（NF）上生长NC/CoxP@NF催化剂，它由CoxP纳米线阵列与氮掺杂碳纳米片（NC）交替生长组成。在制备过程中，Co(OH)2纳米线通过内源Co2+与2−甲基咪唑的溶解配位作用在NF上原位转化为Co-MOF纳米片。仙人掌状的微观结构使NC/CoxP@NF暴露出丰富的活性位点和离子运输通道，促进了HER催化反应动力学。此外，在分级多孔的NC/CoxP@NF中，纳米线和自支撑纳米片交替生长，进一步增强了材料的结构稳定性。最重要的是，表面聚阴离子（磷酸盐）和NC纳米片保护层的形成提高了催化剂的耐腐性能。最终，NC/CoxP@NF-10表现出优异的析氢性能，在1.0 mol L−1 KOH和1.0 mol L−1 KOH + 0.5 mol L−1 NaCl条件下，分别需要107和133 mV的过电位达到10 mA cm−2的电流密度。Abstract: Designing efficient and robust catalysts for hydrogen evolution reaction (HER) is imperative for saline water electrolysis technology. A catalyst composed of CoxP nanowires array with N-doped carbon nanosheets (NC) was fabricated on Ni foam (NF) by an in-situ growth strategy. The material is designated as NC/CoxP@NF. In the preparation process, Co(OH)2 nanowires were transformed into a metal organic framework of cobalt (ZIF-67) on NF by the dissolution-coordination of endogenous Co2+ and 2-methylimidazole. The resulting cactus-like microstructure gives NC/CoxP@NF abundant exposed active sites and ion transport channels, which improve the HER catalytic reaction kinetics. Furthermore, the interconnected alternating nanowires and free-standing nanosheets in NC/CoxP@NF improve its structural stability, and the formation of surface polyanions (phosphate) and a NC nanosheet protective layer improve the anti-corrosive properties of catalysts. Thus, the NC/CoxP@NF has an excellent performance, requiring overpotentials of 107 and 133 mV for HER to achieve 10 mA cm−2 in 1.0 mol L−1 KOH and 1.0 mol L−1 KOH + 0.5 mol L−1 NaCl, respectively. This in-situ transformation strategy is a new way of constructing highly-efficient HER catalysts for saline water electrolysis.
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Figure 1. (a) Schematic illustration of catalysts synthesis. SEM images at different magnifications: (b-d) CoxP@NF; (e-g) NC/CoxP@NF-5; (h-j) NC/CoxP@NF-10 and (k-m) NC/CoxP@NF-15
Figure 2. (a) TEM image; (b) HRTEM image and (c) the corresponding elemental mappings of NC/CoxP@NF-10. (d) XRD patterns and (e) the magnified diffraction peaks at the range of 10°-43° of all catalysts. (f) Raman spectra of NC/CoxP@NF-5, NC/CoxP@NF-10 and NC/CoxP@NF-15. (g) Pore distribution curve of NC/CoxP@NF-10
Figure 3. High-resolution XPS spectra of (a) Co 2p, (b) P 2p, (c) C 1s and (d) N 1s in catalysts
Figure 4. HER performance of all catalysts in 1 mol L−1 KOH solution. (a) Polarization curves. (b) The corresponding Tafel plots. (c) Scan rate dependence of the current densities. (d) EIS Nyquist plots of all electrodes (Inset is the equivalent circuit diagram)
Figure 5. Electrocatalytic HER performance of all catalysts in 1 mol L−1 KOH + 0.5 mol L−1 NaCl. (a) LSV polarization curves. (b) The corresponding Tafel plots. (c) Scan rate dependence of the current densities. (d) EIS Nyquist plots of all electrodes
Figure 6. 1 mol L−1 KOH electrolyte: (a) Chronopotentiometric curves conducted at a constant current density of -100 mA cm−2. The LSV curves before and after stability tests for (b) NC/CoxP@NF-10 and (c) CoxP@NF. 1 mol L−1 KOH + 0.5 mol L−1 NaCl solution: (d) Stability tests of NC/CoxP@NF-10 and CoxP@NF. LSV curves before and after stability tests for (e) NC/CoxP@NF-10 and (f) CoxP@NF
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