Department of Chemistry, Stanford University , Stanford, California 94305, United States.
J Am Chem Soc. 2012 Sep 26;134(38):15849-57. doi: 10.1021/ja305623m. Epub 2012 Sep 17.
Electrocatalyst for oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications and energy-intensive industries. The design and synthesis of highly active ORR catalysts with strong durability at low cost is extremely desirable but remains challenging. Here, we used a simple two-step method to synthesize cobalt oxide/carbon nanotube (CNT) strongly coupled hybrid as efficient ORR catalyst by directly growing nanocrystals on oxidized multiwalled CNTs. The mildly oxidized CNTs provided functional groups on the outer walls to nucleate and anchor nanocrystals, while retaining intact inner walls for highly conducting network. Cobalt oxide was in the form of CoO due to a gas-phase annealing step in NH(3). The resulting CoO/nitrogen-doped CNT (NCNT) hybrid showed high ORR current density that outperformed Co(3)O(4)/graphene hybrid and commercial Pt/C catalyst at medium overpotential, mainly through a 4e reduction pathway. The metal oxide/carbon nanotube hybrid was found to be advantageous over the graphene counterpart in terms of active sites and charge transport. Last, the CoO/NCNT hybrid showed high ORR activity and stability under a highly corrosive condition of 10 M NaOH at 80 °C, demonstrating the potential of strongly coupled inorganic/nanocarbon hybrid as a novel catalyst system in oxygen depolarized cathode for chlor-alkali electrolysis.
用于氧还原反应(ORR)的电催化剂对于各种可再生能源应用和能源密集型产业至关重要。设计和合成具有高活性、强耐久性且低成本的 ORR 催化剂是非常理想的,但极具挑战性。在这里,我们使用一种简单的两步法,通过直接在氧化多壁 CNT 上生长纳米晶体,合成了钴氧化物/碳纳米管(CNT)强耦合的高效 ORR 催化剂。轻度氧化的 CNT 在外壁上提供了功能基团,用于成核和固定纳米晶体,同时保留完整的内壁以形成高导电性网络。由于在 NH(3)中进行了气相退火步骤,因此钴氧化物呈 CoO 形式。所得的 CoO/氮掺杂 CNT(NCNT)杂化物在中等过电势下表现出高的 ORR 电流密度,优于 Co(3)O(4)/石墨烯杂化物和商业 Pt/C 催化剂,主要通过 4e 还原途径。与石墨烯相比,金属氧化物/碳纳米管杂化物在活性位点和电荷输运方面具有优势。最后,CoO/NCNT 杂化物在 80°C 的 10M NaOH 腐蚀性条件下表现出高的 ORR 活性和稳定性,证明了强耦合无机/纳米碳杂化物作为氯碱电解中氧去极化阴极新型催化剂体系的潜力。