Controllable construction of CoP nanoparticles anchored on a nitrogen-doped porous carbon as an electrocatalyst for highly efficient oxygen reduction in Zn-air batteries
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摘要: 为可持续能源设备中的氧还原反应（ORR）探索具有成本效益和高效率的无贵金属催化剂仍然是一项巨大的挑战。在掺杂杂原子的碳上支撑的过渡金属磷化物（TMPs）因其可调的电子结构和更高的催化性能，具有替代贵金属的潜力。本文采用磷化策略（350 °C下二次热解），在分层多孔碳框架（CoP@NC）上构建由掺氮碳壳包裹的CoP纳米颗粒。在二次热解过程中，Co纳米颗粒在NaH2PO2生成的PH3气体下原位转化为CoP纳米颗粒，而载体的十二面体结构没有发生改变。在碱性条件下，CoP@NC电催化剂显示出显著的ORR活性，半波电位高达0.92 V，这归功于分散良好的CoP纳米颗粒、掺氮碳壳之间的协同耦合以及通过多孔结构的高效质量传输。此外，使用CoP@NC电催化剂的锌-空气电池显示1.51 V的高开路电压和210.1 mW cm−2的功率密度。这项研究为开发具有优异ORR性能的低成本催化剂提供了一种新策略，并为燃料电池和金属空气电池的实际应用提供了机会。Abstract: Exploring cost-efficient and high-efficient noble metal-free catalysts for oxygen reduction reactions (ORRs) involved in sustainable energy devices still remains a great challenge. Transition-metal phosphides supported on heteroatom-doped carbons have presented a potential as alternative candidates of precious metals due to their tunable electronic structures and boosted catalytic performance. Herein, phosphating was adopted to construct CoP nanoparticles (NPs) anchored on a nitrogen-doped porous carbon framework (CoP@NC) from Co NPs loaded on NC using PH3 gas released from NaH2PO2 during heat treatment. The dodecahedral structure of Co NPs is retained in their transformation to CoP NPs. The CoP@NC electrocatalyst shows remarkable ORR activity with a half-wave potential up to 0.92 V under alkaline conditions, which is attributed to the synergistic coupling between the well dispersed CoP nanoparticles on the nitrogen-doped carbon support and the efficient mass transport in the porous structure. Zinc-air batteries assembled with the CoP@NC electrocatalyst as an cathode displays a high open-circuit voltage of 1.51 V and power density of 210.1 mW cm−2. This work provides a novel strategy to develop low-cost catalysts with excellent ORR performance to promote their practical application in metal-air batteries.
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Key words:
- Electrocatalysts /
- Co-based catalysts /
- Metal phosphides /
- ORR /
- Zinc-air battery
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Figure 1. SEM micrographs of (a) Co@NC[37] and (b) CoP@NC electrocatalysts. (c) Corresponding XRD patterns. (d-f) TEM images of CoP@NC catalyst
Figure 2. High-resolution deconvoluted XPS analysis of （a） C 1s, (b) N 1s, (c) Co 2p and (d) P 2p
Figure 3. (a) The LSV curves of CoP@NC, Co@NC and Pt/C catalysts. (b) E1/2 and Jk (0.85 V) of different catalysts. (c) Cdl values of each catalyst versus the scanning speed, and the results are drawn as shown. (d) The LSV curves of CoP@NC obtained at rotational speeds of 400-2025 r min−1. (e) K-L plots of CoP@NC. (f) The electron transfer number (n) and the H2O2 selectivity of the CoP@NC and Pt/C catalysts measured according to RRDE. (g) LSV curves before and after 5000 potentiostatic cycles of CoP@NC and Pt/C. (h) chronoamperometric tests of CoP@NC and Pt/C catalys at 0.60 V (vs. RHE). (i) Methanol antitoxicity testing of CoP@NC and Pt/C catalysts.
Figure 4. (a) Open-circuit voltage profile of ZABs under alkaline solution assembled using CoP@NC and Pt/C catalysts as air cathode materials. (Inset) Photograph of connecting two ZABs lighting up a LED. (b) Polarization curves and power density curves of the of ZABs of the CoP@NC and Pt/C catalysts. (c) Discharging capacity curves normalized by the consumed Zn of CoP@NC and Pt/C . (d) Rate performance of ZABs with CoP@NC and Pt/C (20%) as air cathode at 2-20 mA cm−2, respectively. (e) Charge-discharge cycle curves of ZABs using CoP@NC and Pt/C catalysts.
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