Gang Wan

Nitrogen-Doped Carbon Vesicles with Dual Iron-Based Sites for Efficient Oxygen Reduction

A nitrogen-doped vesicle-like porous carbon with well-integrated dual iron-based catalytic sites was developed through direct pyrolysis of inexpensive and abundant precursors. Benefiting from the mesoporous structures with synchronous construction of Fe-Nx and Fe/Fe3 C@NC sites, the optimized catalyst exhibited outstanding performance for the oxygen reduction reaction (ORR) in alkaline media, even superior to the commercial Pt/C catalyst. Detailed characterizations revealed that Fe/Fe3 C@NC sites can make major catalytic contributions in basic media, whereas the Fe-Nx sites were found to play an indispensable role for ORR in acidic media.

Microwave-Assisted Synthesis of Co-Coordinated Hollow Mesoporous Carbon Cubes for Oxygen Reduction Reactions

Transition-metal-/metal-oxide-loaded mesoporous carbon materials with hollow structures are thought to have great potential as catalysts, especially in the areas of sustainable chemistry and energy conversion. However, it is hard to load transition metals/metal oxides onto carbon materials while keeping the carbon materials unchanged through traditional after-treatment processes, thus making it difficult to determine the true roles of the transition metal/metal oxide and carbon in the reactions. Here, Co-coordinated hollow mesoporous carbon cubes (CoMHMCCs) were prepared by a microwave-assisted approach in the presence of ethylene glycol and hollow mesoporous carbon cubes (HMCCs). The synthesized CoMHMCCs inherited most advantages of the HMCCs, such as large surface area and pore volume, uniform pore size distribution, and hollow mesoporous structure, and the Co species was found to coordinate with the N atoms in the N-doped hollow mesoporous carbon cubes. The synthesized CoMHMCCs exhibited a much enhanced oxygen electroreduction reaction activity (∼50 mV deviation from Pt/C), a high selectivity (number of electrons transferred = 3.7-3.9), and excellent electrochemical stability (as low as 12 mV negative shift of half-wave potential after 5000 potential cycles) as a result of a synergetic catalytic effect.

Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis

The introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble-metal-free electrocatalysts for clean energy conversion applications; however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs are investigated for the first time. It is found that the active cobalt-nitrogen sites tend to be selectively constructed on the surface of N-doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt-sites-dependent activity for oxygen reduction reaction and hydrogen evolution reaction in acidic media. The remarkably enhanced catalytic activities approaching that of benchmark Pt/C in an acidic medium have been obtained on the catalyst dominated with cobalt-nitrogen sites, confirmed by the advanced spectroscopic characterization. This finding demonstrates a general paradigm of anion-regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactions related with TMSs.

Engineering Single‐Atom Cobalt Catalysts toward Improved Electrocatalysis

The development of cost-effective catalysts to replace noble metal is attracting increasing interests in many fields of catalysis and energy, and intensive efforts are focused on the integration of transition-metal sites in carbon as noble-metal-free candidates. Recently, the discovery of single-atom dispersed catalyst (SAC) provides a new frontier in heterogeneous catalysis. However, the electrocatalytic application of SAC is still subject to several theoretical and experimental limitations. Further advances depend on a better design of SAC through optimizing its interaction with adsorbates during catalysis. Here, distinctive from previous studies, favorable 3d electronic occupation and enhanced metal-adsorbates interactions in single-atom centers via the construction of nonplanar coordination is achieved, which is confirmed by advanced X-ray spectroscopic and electrochemical studies. The as-designed atomically dispersed cobalt sites within nonplanar coordination show significantly improved catalytic activity and selectivity toward the oxygen reduction reaction, approaching the benchmark Pt-based catalysts. More importantly, the illustration of the active sites in SAC indicates metal-natured catalytic sites and a media-dependent catalytic pathway. Achieving structural and electronic engineering on SAC that promotes its catalytic performances provides a paradigm to bridge the gap between single-atom catalysts design and electrocatalytic applications.

A 3D hierarchical assembly of optimized heterogeneous carbon nanosheets for highly efficient electrocatalysis

A 3D assembly of crumpled nitrogen-doped carbon nanosheets with hierarchical frameworks and encased ultrafine iron carbide nanoparticles on the subunits was constructed via a template-free bottom-up self-assembly strategy. The optimized structure design and catalytic-site integration endow the electrocatalyst with outstanding PH-universal ORR performance, serving as a good alternative for the Pt/C catalyst.

Low Pt-Loaded Mesoporous Sodium Germanate as a High-Performance Electrocatalyst for the Oxygen Reduction Reaction.

Although Pt/C catalysts show relatively high activities for the oxygen reduction reaction (ORR) and great potential for use in polymer electrolyte membrane fuel cells, the large amount of Pt required and the poor stability of Pt/C-based catalysts remain big challenges. Herein, mesoporous Na4 Ge9 O20 micro-crystals have been successfully synthesized to serve as a new kind of electrocatalyst support owing to its special structural characteristics and high structural stability. After loading a low amount of Pt (5 wt %) nanoparticles of 2-5 nm in diameter, the obtained mesoporous Pt/Na4 Ge9 O20 composite shows not only high electrocatalytic activity for ORR in both acidic and alkaline electrolyte media, which are comparable to those of conventional 20 wt % Pt/C, but also remarkably enhanced Pt mass-specified ORR current density and durability. Synergetic catalytic effects between loaded Pt and the support for the ORR activity has been proposed.

Key Single-Atom Electrocatalysis in Metal-Organic Framework (MOF)-Derived Bifunctional Catalysts

Metal-organic framework (MOF)-derived materials have attracted increasing interest and show promising catalytic performances in many fields. Intensive efforts have been focused on the structure design and metal-site integration in MOF-derived catalysts. However, the key catalytic processes related with the metal sites in MOF-derived catalysts that dominate the electrocatalytic performance still remain obscure. Herein, we show a neglected but critical issue in the pyrolytic synthesis of MOF-derived catalysts: the coupled evolution of dual sites, that is, metallic sites and single-atom metal sites. The identification of active sites of single-atom sites from the visible particles has been elucidated through the combined X-ray spectroscopic, electron microscopic, and electrochemical studies. Interestingly, after a total removal of metallic cobalt sites, catalysts with purified single-atom metal sites show no faltering activity for either the oxygen reduction reaction (ORR) or hydrogen evolution reaction (HER), while significantly enhanced ORR selectivity is achieved; this reveals the dominant activity and selectivity contribution from single-atom electrocatalysis. The insight of the coupled evolution of dual sites and the as-demonstrated dual-site decoupling strategies open up a new routine for the design and synthesis of MOF-derived catalysts with the optimized single-atom electrocatalysis towards various electrochemical reactions.

Probing Nitrogen-Doping Effects in the Core-Shell Structured Catalysts for Bifunctional Electrocatalysis.

The design of core‐shell structured catalysts has attracted wide interests due to their remarkable catalytic performances in many fields. Although the nitrogen doping is often integrated in such kind of catalysts, the main contribution is exclusively attributed to the metal sites or the core‐shell configuration. The role of nitrogen doping is often believed to be less important, which remains largely unexplored. Here, in an effort to probe the catalytic role of heterogeneous doping in such core‐shell structure, the effect of nitrogen doping on the activation of cobalt and iron carbide‐based materials for the electrocatalytic reduction of oxygen and the hydrogen evolution reaction is originally revealed. The nitrogen doping in the core‐shell structured biphasic interfaces is found to be of critical importance for triggering the electrocatalytic activity and selectivity. Therefore, this study shows the neglected but critical role of nitrogen doping and biphasic interactions in a core‐shell configuration, paving a new pathway towards the performance enhancement.