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1. Stable and selective electrosynthesis of hydrogen peroxide and the electro-Fenton process on CoSe ₂ polymorph catalysts

   https://doi.org/10.1039/D0EE01925A  

   Sheng, Hongyuan; Janes, Aurora N.; Ross, R. Dominic; Kaiman, Dave; Huang, Jinzhen; Song, Bo; Schmidt, J. R.; Jin, Song (November 2020, Energy & Environmental Science)

   null (Ed.)

   Electrochemical synthesis of hydrogen peroxide (H 2 O 2 ) in acidic solution can enable the electro-Fenton process for decentralized environmental remediation, but robust and inexpensive electrocatalysts for the selective two-electron oxygen reduction reaction (2e − ORR) are lacking. Here, we present a joint computational/experimental study that shows both structural polymorphs of earth-abundant cobalt diselenide (orthorhombic o -CoSe 2 and cubic c -CoSe 2 ) are stable against surface oxidation and catalyst leaching due to the weak O* binding to Se sites, are highly active and selective for the 2e − ORR, and deliver higher kinetic current densities for H 2 O 2 production than the state-of-the-art noble metal or single-atom catalysts in acidic solution. o -CoSe 2 nanowires directly grown on carbon paper electrodes allow for the steady bulk electrosynthesis of H 2 O 2 in 0.05 M H 2 SO 4 with a practically useful accumulated concentration of 547 ppm, the highest among the reported 2e − ORR catalysts in acidic solution. Such efficient and stable H 2 O 2 electrogeneration further enables the effective electro-Fenton process for model organic pollutant degradation. 

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2. 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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3. A Non‐Macrocycle Thiolate‐Based Cobalt Catalyst for Selective O ₂ Reduction into H ₂ O

   https://doi.org/10.1002/cctc.202400270  

   Sun, Lili; Gutierrez, Javier; Goff, Alan Le; Gatineau, David; Jackson, Timothy A; Gennari, Marcello; Duboc, Carole (April 2024, ChemCatChem)

   Abstract The reduction of dioxygen to produce selectively H₂O₂or H₂O is crucial in various fields. While platinum‐based materials excel in 4H⁺/4e⁻oxygen reduction reaction (ORR) catalysis, cost and resource limitations drive the search for cost‐effective and abundant transition metal catalysts. It is thus of great importance to understand how the selectivity and efficiency of 3d‐metal ORR catalysts can be tuned. In this context, we report on a Co complex supported by a bisthiolate N2S2‐donor ligand acting as a homogeneous ORR catalyst in acetonitrile solutions both in the presence of a one‐electron reducing agent (selectivity for H₂O of 93 % and TOFi=3 000 h⁻¹) and under electrochemically‐assisted conditions (0.81 V <η<1.10 V, selectivity for H₂O between 85 % and 95 %). Interestingly, such a predominant 4H⁺/4e⁻pathway for Co‐based ORR catalysts is rare, highlighting the key role of the thiolate donor ligand. Besides, the selectivity of this Co catalyst under chemical ORR conditions is inverse with respect to the Mn and Fe catalysts supported by the same ligand, which evidences the impact of the nature of the metal ion on the ORR selectivity. 

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4. Aqueous Photoelectrochemical CO ₂ Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst

   https://doi.org/10.1002/anie.202215213  

   Shang, Bo; Rooney, Conor L.; Gallagher, David J.; Wang, Bernie T.; Krayev, Andrey; Shema, Hadar; Leitner, Oliver; Harmon, Nia J.; Xiao, Langqiu; Sheehan, Colton; et al (January 2023, Angewandte Chemie International Edition)

   Abstract We report a precious‐metal‐free molecular catalyst‐based photocathode that is active for aqueous CO 2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3‐aminopropyl)triethoxysilane linker to p‐type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO 2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of −0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s −1 . To date, this is the only molecular catalyst‐based photoelectrode that is active for the six‐electron reduction of CO 2 to methanol. This work puts forth a strategy for interfacing molecular catalysts to p‐type semiconductors and demonstrates state‐of‐the‐art performance for photoelectrochemical CO 2 reduction to CO and methanol. 

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5. Highly Selective Oxygen Reduction to Hydrogen Peroxide on a Carbon-Supported Single-Atom Pd Electrocatalyst

   https://doi.org/10.1021/acscatal.1c05633  

   Wang, Nan; Zhao, Xunhua; Zhang, Rui; Yu, Saerom; Levell, Zachary H.; Wang, Chunyang; Ma, Shaobo; Zou, Peichao; Han, Lili; Qin, Jiayi; et al (March 2022, ACS Catalysis)

   Selective electrochemical two-electron oxygen reduction is a promising route for renewable and on-site H2O2 generation as an alternative to the anthraquinone process. Herein, we report a high-performance nitrogen-coordinated single-atom Pd electrocatalyst, which is derived from Pd-doped zeolitic imidazolate frameworks (ZIFs) through one-step thermolysis. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with X-ray absorption spectroscopy verifies atomically dispersed Pd atoms on nitrogen-doped carbon (Pd-NC). The single-atom Pd-NC catalyst exhibits excellent electrocatalytic performance for two-electron oxygen reduction to H2O2, which shows ∼95% selectivity toward H2O2 and an unprecedented onset potential of ∼0.8 V versus revisable hydrogen electrode (RHE) in 0.1 M KOH. Density functional theory (DFT) calculations demonstrate that the Pd-N4 catalytic sites thermodynamically prefer *–O bond breaking to O–O bond breaking, corresponding to a high selectivity for H2O2 production. This work provides a deep insight into the understanding of the catalytic process and design of high-performance 2e– ORR catalysts. 

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