TY - GEN A1 - Braga, Daniel S. A1 - Pedersen, Angus A1 - Riyaz, Mohd A1 - Barrio, Jesús A1 - Bagger, Alexander A1 - Neckel, Itamar T. A1 - Mariano, Thiago M. A1 - Winkler, Manuel E. G. A1 - Stephens, Ifan E. L. A1 - Titirici, Maria‐Magdalena A1 - Nagao, Raphael T1 - Inside back cover image for the article "In situ structural evolution and activity descriptor of atomically dispersed catalysts during nitrate electroreduction" N2 - This cover illustrates the electrosynthesis of ammonia through the reduction of nitrate ions on metallic clusters formed from single atom catalysts. The artwork highlights the catalytic interface where molecular transformations occur, linking nanoscale reactions to sustainable fertilizer production. By converting pollutants into value-added products, this work envisions a green pathway toward circular nitrogen management and enhanced agricultural sustainability. More details can be found in the Research Article (DOI: 10.1002/advs.202510282) by Maria-Magdalena Titirici, Raphael Nagao, and co-workers. KW - Single atom KW - Nitrate reduction KW - In situ KW - Structure-activity-selectivity PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-652626 DO - https://doi.org/10.1002/advs.71951 SN - 2198-3844 VL - 12 IS - 39 SP - 1 PB - Wiley-VCH CY - Weinheim AN - OPUS4-65262 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Castells-Gil, Javier A1 - Zhu, Jinjie A1 - Itskou, Ioanna A1 - Wolpert, Emma H. A1 - Hunter, Robert D. A1 - Tidey, Jeremiah P. A1 - Pedersen, Angus A1 - Solvay, Elisa A1 - Tyrrell, Helen A1 - Petit, Camille A1 - Barrio, Jesús T1 - Impact of N-heterocyclic amine modulators on the structure and thermal conversion of a zeolitic imidazole framework N2 - 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. KW - Zeolitic imidazole framework KW - Heterocyclic amine KW - Triaminopyrimidine PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-639177 DO - https://doi.org/10.1039/D5TA04831A SN - 2050-7488 SP - 1 EP - 13 PB - Royal Society of Chemistry (RSC) AN - OPUS4-63917 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Braga, Daniel S. A1 - Pedersen, Angus A1 - Riyaz, Mohd A1 - Barrio, Jesús A1 - Bagger, Alexander A1 - Neckel, Itamar T. A1 - Mariano, Thiago M. A1 - Winkler, Manuel E. G. A1 - Stephens, Ifan E. L. A1 - Titirici, Maria‐Magdalena A1 - Nagao, Raphael T1 - In situ structural evolution and activity descriptor of atomically dispersed catalysts during nitrate electroreduction N2 - Single‐Atom Catalysts (SAC) have emerged as a promising class of materials for various catalytic applications, including the electrochemical nitrate reduction reaction (eNO3RR) and consequently ammonia production. While the efficiency and selectivity of these materials have been extensively highlighted for the eNO3RR, the in situ evolution to their structure and composition during electrocatalysis is largely unexplored and lacks catalyst design principles. To solve this, we investigated a series of high utilization metal‐nitrogen‐carbon (MNC) SACs (M = Cr, Fe, Co, Ni, and Cu) for eNO3RR. Except for CuNC, which selectively produced nitrite, all catalysts exhibited Faradaic efficiencies (FE) for ammonia exceeding 50%. NiNC demonstrated the highest performance (FE of 78.0 ± 2.9% at −0.4 V versus reversible hydrogen electrode (RHE) at pH 13 and maximum ammonia production rate of 615.7 ± 176.5 µmol·h−1·, corresponding to an energy efficiency of 15.1 ± 1.4% at −0.6 VRHE), followed by CoNC. In situ Synchrotron X‐ray fluorescence (SXRF) mapping at various cathodic potentials (from open circuit potential to 0.0 VRHE and then −0.6 VRHE at 100 mV steps) revealed significant mobility of Ni within the carbon matrix, leading to the formation of metallic clusters from 0.0 VRHE. Similar in situ metal clustering is observed for CoNC. Structure‐activity plots are generated from both MNC literature and results obtained here, finding a clear trend between OH binding energy and turnover frequency, with the high activity of NiNC and CoNC in this work explained by their stronger OH binding in the metallic structure compared to their SAC coordination. This work therefore, reveals the structure‐activity‐stability of MNCs for eNO3RR and provides a simple descriptor for identifying highly active eNO3RR catalysts and their in situ structural evolution. KW - Single atom KW - Nitrate reduction KW - Structure-activity-selectivity KW - In situ PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-640353 DO - https://doi.org/10.1002/advs.202510282 SN - 2198-3844 VL - 12 IS - 39 SP - 1 EP - 14 PB - Wiley-VCH CY - Weinheim AN - OPUS4-64035 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Petitdemange, Eliot A1 - Zhu, Jinjie A1 - Pedersen, Angus A1 - Parker, Joseph A1 - Balaghi, Esmael A1 - Li, Shaohua A1 - Favero, Silvia A1 - Ignacio Martínez, José A1 - Haigh, Sarah A1 - Titirici, Maria-Magdalena A1 - Fischer, Anna A1 - Barrio, Jesús T1 - High-Yield Synthesis of Fe-NC Electrocatalysts Using Mg2+ Templating and Schiff-Base Porous Organic Polymers N2 - 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. KW - Porous Organic Polymers KW - Single Atom KW - Oxygen reduction PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-652618 DO - https://doi.org/10.1002/adfm.202518944 SN - 1616-3028 SP - 1 EP - 15 PB - Wiley-VCH GmbH AN - OPUS4-65261 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pedersen, Angus A1 - Zhu, Jinjie A1 - Barrio, Jesús A1 - Parker, Joseph A1 - Hunter, Robert D. A1 - Haigh, Sarah J. A1 - Fellinger, Tim-Patrick A1 - Stephens, Ifan E. L. A1 - Titirici, Maria-Magdalena T1 - Contribution of Mg-templated porosity to activity and durability in Fe–N–C O 2 reduction catalysts N2 - 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. KW - Porosity KW - Single atom KW - Oxygen reduction PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-657549 DO - https://doi.org/10.1039/d5ma01488c SN - 2633-5409 SP - 1 EP - 8 PB - Royal Society of Chemistry (RSC) AN - OPUS4-65754 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -