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1. Altering Ligand Fields in Single-Atom Sites through Second-Shell Anion Modulation Boosts the Oxygen Reduction Reaction

   https://doi.org/10.1021/jacs.1c11331  

   Qin, Jiayi; Liu, Hui; Zou, Peichao; Zhang, Rui; Wang, Chunyang; Xin, Huolin L. (January 2022, Journal of the American Chemical Society)

   Single-atom catalysts based on metal–N4 moieties and anchored on carbon supports (defined as M–N–C) are promising for oxygen reduction reaction (ORR). Among those, M–N–C catalysts with 4d and 5d transition metal (TM4d,5d) centers are much more durable and not susceptible to the undesirable Fenton reaction, especially compared with 3d transition metal based ones. However, the ORR activity of these TM4d,5d–N–C catalysts is still far from satisfactory; thus far, there are few discussions about how to accurately tune the ligand fields of single-atom TM4d,5d sites in order to improve their catalytic properties. Herein, we leverage single-atom Ru–N–C as a model system and report an S-anion coordination strategy to modulate the catalyst’s structure and ORR performance. The S anions are identified to bond with N atoms in the second coordination shell of Ru centers, which allows us to manipulate the electronic configuration of central Ru sites. The S-anion-coordinated Ru–N–C catalyst delivers not only promising ORR activity but also outstanding long-term durability, superior to those of commercial Pt/C and most of the near-term single-atom catalysts. DFT calculations reveal that the high ORR activity is attributed to the lower adsorption energy of ORR intermediates at Ru sites. Metal–air batteries using this catalyst in the cathode side also exhibit fast kinetics and excellent stability. 

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2. Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells

   https://doi.org/10.1039/d0ee01968b  

   Shi, Qiurong; He, Yanghua; Bai, Xiaowan; Wang, Maoyu; Cullen, David A.; Lucero, Macros; Zhao, Xunhua; More, Karren L.; Zhou, Hua; Feng, Zhenxing; et al (January 2020, Energy & Environmental Science)

   Proton-exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are promising power sources from portable electronic devices to vehicles. The high-cost issue of these low-temperature fuel cells can be primarily addressed by using platinum-group metal (PGM)-free oxygen reduction reaction (ORR) catalysts, in particular atomically dispersed metal–nitrogen–carbon (M–N–C, M = Fe, Co, Mn). Furthermore, a significant advantage of M–N–C catalysts is their superior methanol tolerance over Pt, which can mitigate the methanol cross-over effect and offer great potential of using a higher concentration of methanol in DMFCs. Here, we investigated the ORR catalytic properties of M–N–C catalysts in methanol-containing acidic electrolytes via experiments and density functional theory (DFT) calculations. FeN 4 sites demonstrated the highest methanol tolerance ability when compared to metal-free pyridinic N, CoN 4 , and MnN 4 active sites. The methanol adsorption on MN 4 sites is even strengthened when electrode potentials are applied during the ORR. The negative influence of methanol adsorption becomes significant for methanol concentrations higher than 2.0 M. However, the methanol adsorption does not affect the 4e − ORR pathway or chemically destroy the FeN 4 sites. The understanding of the methanol-induced ORR activity loss guides the design of promising M–N–C cathode catalyst in DMFCs. Accordingly, we developed a dual-metal site Fe/Co–N–C catalyst through a combined chemical-doping and adsorption strategy. Instead of generating a possible synergistic effect, the introduced Co atoms in the first doping step act as “scissors” for Zn removal in metal–organic frameworks (MOFs), which is crucial for modifying the porosity of the catalyst and providing more defects for stabilizing the active FeN 4 sites generated in the second adsorption step. The Fe/Co–N–C catalyst significantly improved the ORR catalytic activity and delivered remarkably enhanced peak power densities ( i.e. , 502 and 135 mW cm −2 ) under H 2 –air and methanol–air conditions, respectively, representing the best performance for both types of fuel cells. Notably, the fundamental understanding of methanol tolerance, along with the encouraging DMFC performance, will open an avenue for the potential application of atomically dispersed M–N–C catalysts in other direct alcohol or ammonia fuel cells. 

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3. Direct Conversion of MnO ₂ into Atomic Mn Sites for Oxygen Reduction

   https://doi.org/10.1149/1945-7111/ae2b11  

   Yang, Xiaoxuan; Chen, Mengjie; Wang, Maoyu; Feng, Zhenxing; Shao, Yuyan; Wu, Gang (December 2025, Journal of The Electrochemical Society)

   Atomic metal sites, such as Fe, Co, and Mn, coordinated with N and embedded in carbon, are the most promising platinum-group-metal (PGM)-free catalysts for acidic oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells. Among others, Mn sites are preferable to minimize potential Fenton reactions within the electrode. Herein, we demonstrate a facile and scalable synthetic method to prepare atomic Mn-N-C catalysts by directly converting manganese oxides into active, stable MnN₄sites via solid-state reactions. Post-treatment with ammonium chloride can enhance the intrinsic ORR activity of MnN_xmoieties by introducing additional nitrogen groups and defects. Subsequent post-treatment with organic molecules, such as benzimidazole, promotes the formation of a robust carbon structure and significantly improves catalyst stability. The resulting Mn-N-C catalyst exhibits promising ORR activity, achieving a half-wave potential of 0.83 VvsRHE in aqueous 0.5 M H₂SO₄electrolyte, outperforming most PGM-free ORR catalysts. A corresponding membrane electrode assembly (MEA) generated a current density of ∼400 mA cm⁻²at 0.67 V and a peak power density of 0.46 W cm⁻². Significantly, post-treatment with benzimidazole improved catalyst stability, retaining 85% of the MEA performance, although the initial performance was compromised. 

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4. Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement

   https://doi.org/10.1039/C9CS00903E  

   He, Yanghua; Liu, Shengwen; Priest, Cameron; Shi, Qiurong; Wu, Gang (June 2020, Chemical Society Reviews)

   The urgent need to address the high-cost issue of proton-exchange membrane fuel cell (PEMFC) technologies, particularly for transportation applications, drives the development of simultaneously highly active and durable platinum group metal-free (PGM-free) catalysts and electrodes. The past decade has witnessed remarkable progress in exploring PGM-free cathode catalysts for the oxygen reduction reaction (ORR) to overcome sluggish kinetics and catalyst instability in acids. Among others, scientists have identified the newly emerging atomically dispersed transition metal (M: Fe, Co, or/and Mn) and nitrogen co-doped carbon (M–N–C) catalysts as the most promising alternative to PGM catalysts. Here, we provide a comprehensive review of significant breakthroughs, remaining challenges, and perspectives regarding the M–N–C catalysts in terms of catalyst activity, stability, and membrane electrode assembly (MEA) performance. A variety of novel synthetic strategies demonstrated effectiveness in improving intrinsic activity, increasing active site density, and attaining optimal porous structures of catalysts. Rationally designing and engineering the coordination environment of single metal MN x sites and their local structures are crucial for enhancing intrinsic activity. Increasing the site density relies on the innovative strategies of restricting the migration and agglomeration of single metal sites into metallic clusters. Relevant understandings provide the correlations among the nature of active sites, nanostructures, and catalytic activity of M–N–C catalysts at the atomic scale through a combination of experimentation and theory. Current knowledge of the transferring catalytic properties of M–N–C catalysts to MEA performance is limited. Rationally designing morphologic features of M–N–C catalysts play a vital role in boosting electrode performance through exposing more accessible active sites, realizing uniform ionomer distribution, and facilitating mass/proton transports. We outline future research directions concerning the comprehensive evaluation of M–N–C catalysts in MEAs. The most considerable challenge of current M–N–C catalysts is the unsatisfied stability and rapid performance degradation in MEAs. Therefore, we further discuss practical methods and strategies to mitigate catalyst and electrode degradation, which is fundamentally essential to make M–N–C catalysts viable in PEMFC technologies. 

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5. High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites

   https://doi.org/10.1039/C9EE00877B  

   Zhang, Hanguang; Chung, Hoon T.; Cullen, David A.; Wagner, Stephan; Kramm, Ulrike I.; More, Karren L.; Zelenay, Piotr; Wu, Gang (August 2019, Energy & Environmental Science)

   Platinum group metal-free (PGM-free) catalysts for the oxygen reduction reaction (ORR) with atomically dispersed FeN 4 sites have emerged as a potential replacement for low-PGM catalysts in acidic polymer electrolyte fuel cells (PEFCs). In this work, we carefully tuned the doped Fe content in zeolitic imidazolate framework (ZIF)-8 precursors and achieved complete atomic dispersion of FeN 4 sites, the sole Fe species in the catalyst based on Mößbauer spectroscopy data. The Fe–N–C catalyst with the highest density of active sites achieved respectable ORR activity in rotating disk electrode (RDE) testing with a half-wave potential ( E 1/2 ) of 0.88 ± 0.01 V vs. the reversible hydrogen electrode (RHE) in 0.5 M H 2 SO 4 electrolyte. The activity degradation was found to be more significant when holding the potential at 0.85 V relative to standard potential cycling (0.6–1.0 V) in O 2 saturated acid electrolyte. The post-mortem electron microscopy analysis provides insights into possible catalyst degradation mechanisms associated with Fe–N coordination cleavage and carbon corrosion. High ORR activity was confirmed in fuel cell testing, which also divulged the promising performance of the catalysts at practical PEFC voltages. We conclude that the key factor behind the high ORR activity of the Fe–N–C catalyst is the optimum Fe content in the ZIF-8 precursor. While too little Fe in the precursors results in an insufficient density of FeN 4 sites, too much Fe leads to the formation of clusters and an ensuing significant loss in catalytic activity due to the loss of atomically dispersed Fe to inactive clusters or even nanoparticles. Advanced electron microscopy was used to obtain insights into the clustering of Fe atoms as a function of the doped Fe content. The Fe content in the precursor also affects other key catalyst properties such as the particle size, porosity, nitrogen-doping level, and carbon microstructure. Thanks to using model catalysts exclusively containing FeN 4 sites, it was possible to directly correlate the ORR activity with the density of FeN 4 species in the catalyst. 

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