Catalytic Activity for ORR of Pt Supported on Ordered Mesoporous Carbon with Network Structure
Authors: Miyao Toshihiro , Nishino Hanako , Yamazaki Hiroko , Sato Satoko , Tamoto Kayoko , Uchida Makoto , Iiyama Akihiro , Shibanuma Kazuya , Koizumi Naoto 
Published: November 2022

Introduction
In order to realize carbon neutrality, working toward becoming a hydrogen-based society using renewable energy is essential, and hydrogen fuel cell vehicles will be one of the key devices. For further widespread deployment of fuel cell vehicles, cost reduction and performance enhancement of polymer electrolyte fuel cell (PEFC) systems are urgently needed. Recently, Pt/C-based electrocatalysts using mesoporous carbon as a support material have attracted attention, because well-designed mesopores can act as “accessible pores,” in which direct contact between ionomer and Pt surface is avoided, while the transport of protons, oxygen and generated water is not suppressed. Ordered mesoporous carbon (OMC) with a uniform nanopore structure is one of the ideal candidate materials for a catalyst support with accessible pores. However, with conventional synthesis methods, the typical OMC primary particle size is on the order of micrometers, and mass transport within the nanopores could be a difficult issue. In the present study, we focused on the development of OMC nanoparticles with a network structure. By use of nonionic surfactant micelles with phenol-formaldehyde resole resin as a carbon source, we obtained OMC nanoparticles with a novel hierarchical network structure (ns-OMC). To the best of our knowledge, there are no reports of the synthesis of ordered mesoporous carbon nanoparticles with a rigid network structure. In this study, in addition to the effect of synthesis conditions on the ns-OMC structure, a newly developed technique for the selective deposition of Pt nanoparticles within the ns-OMC nanopores, and the ORR activity of the Pt/ns-OMC catalysts, will be discussed in detail.
Experimental
Ns-OMC powder was synthesized with resol-nonionic surfactant micelles as a carbon source and structure directing agent. Resol-F127 (nonionic surfactant) micelles were synthesized by mixing phenol, formaldehyde, water and F127 with sodium hydroxide. After hydrothermal treatment of the mixture, the resulting solid was filtered and washed thoroughly and dried under vacuum. The obtained powder was carbonized at 700 ºC followed by annealing at 1000 ºC. Pt was deposited on the ns-OMC powder by the reverse micelle and colloid techniques. Cyclic voltammetry and linear sweep voltammetry were carried out in N2-saturated and O2-saturated 0.1 M HClO4 solution at 25 ºC using the conventional rotating disk electrode (RDE) technique. Potential step cycling measurements simulating load cycling between 0.6 V and 1.0 V vs. RHE were carried out according to the FCCJ protocol. Coating of the catalyst on a glassy carbon disk substrate was carried out by an electrospray (ES) coating technique developed by our group [1]. N2 adsorption measurement at liquid nitrogen temperature was carried out. The morphology of the Pt/ns-OMC was observed by scanning transmission electron microscope (STEM).
Results and discussion
As seen in the STEM images of the ns-OMC powder (Figure 1), the network structure formed by connection of OMC primary nanoparticles to form developed macropores is clearly observed. The OMC nanoparticles were tightly connected via a thick necking structure. The primary particle size of the OMC and neck thickness were controllable via the resol-F127 micelle concentration and the temperature during the hydrothermal treatment. Highly ordered nanopores were observed on the surface of the OMC particles, with a pore size of ca. 5 nm and an interpore distance of ca. 8 nm. The nanopores and the network structure were stable even after high temperature annealing at 1400 ºC. The BET specific surface area for the ns-OMC annealed at 1000 ºC was 814 m2 g-1, and the BJH pore size distribution curve of the ns-OMC showed a mesopore peak at 4.5 nm, which is in good agreement with the STEM observation. When Pt was deposited on the ns-OMC support, most of the Pt particles, with diameters of 4 to 5 nm, were dispersed on the support and, interestingly, located inside or right above the nanopore entrances. Careful STEM measurements revealed that the Pt particles were not deposited deeply within the OMC nanopores, but most were deposited at relatively shallow positions. RDE measurements revealed that the Pt/ns-OMC catalysts showed higher specific activity and mass activity for the ORR and much higher stability for the ECSA values during potential step cycling measurements in comparison with a commercial Pt/CB catalyst. The higher catalytic activity and durability observed for the Pt/ns-OMC catalyst may be due to a near-ideal distance between neighboring Pt particles deposited on the novel support. Aggregation and sintering of the Pt particles were successfully suppressed due to the nanopore structure.
[1] S. Cho, K. Tamoto and M. Uchida, Energy Fuels, 34, 14853 (2020).
Acknowledgement: This work was supported by the ECCEED’30-FC project from NEDO.

Figure 1