Qiao Yu, Ni Yangyang, Kong Fantan, Li Ruijing, Zhang Chaoqi, Kong Aiguo, Shan Yongkui
School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai, 200241, P. R. China.
Chem Asian J. 2019 Aug 1;14(15):2676-2684. doi: 10.1002/asia.201900524. Epub 2019 Jun 26.
Well-dispersed carbon-coated or nitrogen-doped carbon-coated copper-iron alloy nanoparticles (FeCu@C or FeCu@C-N) in carbon-based supports are obtained using a bimetallic metal-organic framework (Cu/Fe-MOF-74) or a mixture of Cu/Fe-MOF-74 and melamine as sacrificial templates and an active-component precursor by using a pyrolysis method. The investigation results attest formation of Cu-Fe alloy nanoparticles. The obtained FeCu@C catalyst exhibits a catalytic activity with a half-wave potential of 0.83 V for oxygen reduction reaction (ORR) in alkaline medium, comparable to that on commercial Pt/C catalyst (0.84 V). The catalytic activity of FeCu@C-N for ORR (E =0.87 V) outshines all reported analogues. The excellent performance of FeCu@C-N should be attributed to a change in the energy of the d-band center of Cu resulting from the formation of the copper-iron alloy, the interaction between alloy nanoparticles and supports and N-doping in the carbon matrix. Moreover, FeCu@C and FeCu@C-N show better electrochemical stability and methanol tolerance than commercial Pt/C and are expected to be widely used in practical applications.
通过使用双金属金属有机框架（Cu/Fe-MOF-74）或Cu/Fe-MOF-74与三聚氰胺的混合物作为牺牲模板和活性组分前驱体，采用热解方法，在碳基载体中获得了分散良好的碳包覆或氮掺杂碳包覆的铜铁合金纳米颗粒（FeCu@C或FeCu@C-N）。研究结果证实了Cu-Fe合金纳米颗粒的形成。所制备的FeCu@C催化剂在碱性介质中对氧还原反应（ORR）表现出催化活性，半波电位为0.83 V，与商业Pt/C催化剂（0.84 V）相当。FeCu@C-N对ORR的催化活性（E = 0.87 V）优于所有已报道的类似物。FeCu@C-N的优异性能应归因于铜铁合金形成导致的Cu的d带中心能量变化、合金纳米颗粒与载体之间的相互作用以及碳基体中的N掺杂。此外，FeCu@C和FeCu@C-N比商业Pt/C表现出更好的电化学稳定性和甲醇耐受性，有望在实际应用中得到广泛应用。
