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- Oxygen reduction (2)
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Organisationseinheit der BAM
The zeolitic imidazole framework-8 (ZIF-8) is a crystalline porous material that has been widely employed as template to fabricate porous nitrogen-doped carbons with high microporosity via thermal treatment at high temperatures. The properties of the carbon scaffold are influenced by the pore structure and chemical composition of the parent ZIF. However, the narrow pore size distribution and microporous nature from ZIF-8 often results in low mesopore volume, which is crucial for applications such as energy storage and conversion. Here we show that insertion of N-heterocyclic amines can disrupt the structure of ZIF-8 and dramatically impact the chemical composition and pore structure of the nitrogen-doped carbon frameworks obtained after high-temperature pyrolysis. Melamine and 2,4,6-triaminopyrimidine were chosen to modify the ZIF-8 structure owing to their capability to both coordinate metal ions and establish supramolecular interactions. Employing a wide variety of physical characterization techniques we observed that melamine results in the formation of a mixed-phase material comprising ZIF-8, Zn(Ac)6(Mel)2 and crystallized melamine, while 2,4,6-triaminopyrimidine induces the formation of defects, altering the pore structure. Furthermore, the absence of heterocyclic amine in the ZIF-8 synthesis leads to a new crystalline phase, unreported to date. The thermal conversion of the modified ZIFs at 1000 °C leads to nitrogen-doped carbons bearing Zn moieties with increased surface area, mesopore volume and varying degree of defects compared to ZIF-8 derived carbon. This work therefore highlights both the versatility of heterocyclic amines to modify the structure of framework materials as well as their role in tuning pore structure in nitrogen-doped carbons, paving the way to targeted design of high-performance electrodes for energy storage and conversion.
The decoupled synthesis of Fe-NC single-site electrocatalysts mediated by Lewis acids enables high active site density and utilization. However, current approaches often rely on small organic molecules and suffer from low synthesis yields due to the high Lewis acid-to-precursor ratios required to achieve highly porous carbons. Here, a porous organic polymer (POP) based on 2,4,6-Triaminopyrimidine (TAP) is utilized as a carbon-nitrogen-based scaffold for the synthesis of Fe─NC electrocatalysts. By tuning the amounts of MgCl2 ·6H2O used both as porogen and active site templating agent, synthetic yields exceeding 45% are achieved, a significant improvement compared to the 6% yield from the molecular analogue and the highest reported forMg2+ templated systems. Subsequent low-temperature exchange with Fe leads to atomically dispersed FeNx, minimizing Fe aggregation. The resulting materials exhibit high specific surface areas (>1000 m2 g−1) with micro-, meso-, and macropores, which promote mass transport and active site accessibility. Compared to Fe─NC synthesized via direct pyrolysis of Fe-coordinated POP, the decoupled method enables significantly higher catalytic activity in both alkaline and acidic media, and delivers 1 A cm−2 at 0.687 ± 0.004 VRHE in an alkaline gas diffusion electrode, highlighting its potential for practical oxygen reduction devices.
Atomically dispersed Fe in N-doped carbon (Fe–N–C) catalysts are leading platinum-group-metal-free candidates for the O2 reduction reaction in proton exchange membrane fuel cells (PEMFCs). Zeolitic imidazolate framework (ZIF-8) derived Fe–N–C present the most promising performance; however, they possess a narrow distribution of small micropores, which limits active site accessibility. Here, to induce hierarchical porosity in Fe–N–C, we report a systematic study on MgCl2·6H2O-templated ZIF-8-derived Fe–N–C catalysts for the O2 reduction reaction. MgCl2·6H2O addition induced complete Zn removal, collapse of the ZIF-8 framework, and formation of large micro- and mesopores, with graphene-like structures. N content was markedly reduced, with conversion from pyridinic to pyrrolic N species. Rotating disc electrode tests showed a progressive increase in O2 reduction activity with MgCl2·6H2O, which is strongly correlated (R2 = 0.98) to the formation of large micropores and small mesopores (1–4 nm). This introduces an indirect structure–activity design principle for Fe–N–Cs. The enhanced Fe–N–C porosity also leads to increased degradation rates under accelerated stress test conditions, which we attributed to the oxidation of disordered carbon domains and active Fe loss. This study highlights a key trade-off between porosity-driven O2 reduction activity and durability in Fe–N–C catalysts.
