Jing Li, Quansong Zhu, Alvin Chang, Seonjeong Cheon, Yuanzuo Gao, Bo Shang, Huan Li, Conor L. Rooney, Longtao Ren, Zhan Jiang, Yongye Liang, Zhenxing Feng, Shize Yang, L. Robert Baker, Hailiang Wang
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引用次数: 0
摘要
酞菁钴（CoPc）催化电化学将二氧化碳还原成甲醇的法拉第效率很高，但容易失活。四氨基酞菁钴（CoPc-NH2）的稳定性有所提高，但其甲醇法拉第效率低于 30%。本研究通过合理设计双位点级联催化剂，解决了这些在选择性、反应性和稳定性方面的局限性。在此，我们对工作中的 CoPc-NH2 催化剂附近的 CO（反应的关键中间产物）局部浓度进行了量化，并表明在多壁碳纳米管上共负载四甲氧基酞菁镍（NiPc-OCH3）与 CoPc-NH2 可增加 CO 的生成和局部浓度。这种双位点级联催化剂的性能大大高于原始的单位点 CoPc-NH2/ 碳纳米管催化剂，在甲醇生产中的部分电流密度达到 150 mA cm-2，法拉第效率达到 50%。动力学分析和原位和频发生振动光谱将这种显著的性能改进归因于分子尺度的 CO 从 NiPc-OCH3 位点溢出到具有甲醇活性的 CoPc-NH2 位点。
Molecular-scale CO spillover on a dual-site electrocatalyst enhances methanol production from CO2 reduction
Cobalt phthalocyanine (CoPc) is recognized for catalysing electrochemical CO2 reduction into methanol at high Faradaic efficiency but is subject to deactivation. Cobalt tetraaminophthalocyanine (CoPc-NH2) shows improved stability, but its methanol Faradaic efficiency is below 30%. This study addresses these limitations in selectivity, reactivity and stability by rationally designing a dual-site cascade catalyst. Here we quantify the local concentration of CO, a key intermediate of the reaction, near a working CoPc-NH2 catalyst and show that co-loading nickel tetramethoxyphthalocyanine (NiPc-OCH3) with CoPc-NH2 on multiwalled carbon nanotubes increases the generation and local concentration of CO. This dual-site cascade catalyst exhibits substantially higher performance than the original single-site CoPc-NH2/carbon nanotube catalyst, reaching a partial current density of 150 mA cm−2 and a Faradaic efficiency of 50% for methanol production. Kinetic analysis and in situ sum-frequency generation vibrational spectroscopy attribute this notable performance improvement to molecular-scale CO spillover from NiPc-OCH3 sites to methanol-active CoPc-NH2 sites.
期刊介绍：
Nature Nanotechnology is a prestigious journal that publishes high-quality papers in various areas of nanoscience and nanotechnology. The journal focuses on the design, characterization, and production of structures, devices, and systems that manipulate and control materials at atomic, molecular, and macromolecular scales. It encompasses both bottom-up and top-down approaches, as well as their combinations.
Furthermore, Nature Nanotechnology fosters the exchange of ideas among researchers from diverse disciplines such as chemistry, physics, material science, biomedical research, engineering, and more. It promotes collaboration at the forefront of this multidisciplinary field. The journal covers a wide range of topics, from fundamental research in physics, chemistry, and biology, including computational work and simulations, to the development of innovative devices and technologies for various industrial sectors such as information technology, medicine, manufacturing, high-performance materials, energy, and environmental technologies. It includes coverage of organic, inorganic, and hybrid materials.
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