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1. Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination

   https://doi.org/10.1038/s41467-019-11992-2  

   Jiang, Kun ; Back, Seoin ; Akey, Austin J. ; Xia, Chuan ; Hu, Yongfeng ; Liang, Wentao ; Schaak, Diane ; Stavitski, Eli ; Nørskov, Jens K. ; Siahrostami, Samira ; et al ( September 2019 , Nature Communications)

   Shifting electrochemical oxygen reduction towards 2e^–pathway to hydrogen peroxide (H₂O₂), instead of the traditional 4e^–to water, becomes increasingly important as a green method for H₂O₂generation. Here, through a flexible control of oxygen reduction pathways on different transition metal single atom coordination in carbon nanotube, we discovered Fe-C-O as an efficient H₂O₂catalyst, with an unprecedented onset of 0.822 V versus reversible hydrogen electrode in 0.1 M KOH to deliver 0.1 mA cm⁻²H₂O₂current, and a high H₂O₂selectivity of above 95% in both alkaline and neutral pH. A wide range tuning of 2e^–/4e^–ORR pathways was achieved via different metal centers or neighboring metalloid coordination. Density functional theory calculations indicate that the Fe-C-O motifs, in a sharp contrast to the well-known Fe-C-N for 4e^–, are responsible for the H₂O₂pathway. This iron single atom catalyst demonstrated an effective water disinfection as a representative application.

    

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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. Electrocatalytic production of hydrogen peroxide enabled by post-synthetic modification of a self-assembled porphyrin cube

   https://doi.org/10.1039/d2qi02050e  

   Crawley, Matthew R. ; Zhang, Daoyang ; Cook, Timothy R. ( December 2022 , Inorganic Chemistry Frontiers)

   Self-assembled metallacyles and cages formed via coordination chemistry have been used as catalysts to enforce 4H + /4e − reduction of oxygen to water with an emphasis on attenuating the formation of hydrogen peroxide. That said, the kinetically favored 2H + /2e − reduction to H 2 O 2 is critically important to industry. In this work we report the synthesis, characterization, and electrochemical benchmarking of a hexa-porphyrin cube which catalyses the electrochemical reduction of molecular oxygen to hydrogen peroxide. An established sub-component self-assembly approach was used to synthesize the cubic free-base porphryin topologies from 2-pyridinecarboxaldehyde, tetra-4-aminophenylporphryin (TAPP), and Fe(OTf) 2 (OTf − = trifluoromethansulfonate). Then, a tandem metalation/transmetallation was used to introduce Co( ii ) into the porphyrin faces of the cube, and exchange with the Fe( ii ) cations at the vertices, furnishing a tetrakaideca cobalt cage. Electron paramagnetic resonance studies on a Cu( ii )/Fe( ii ) analogue probed radical interactions which inform on electronic structure. The efficacy and selectivity of the CoCo-cube as a catalyst for hydrogen peroxide generation was investigated using hydrodynamic voltammetry, revealing a higher selectivity than that of a mononuclear Co( ii ) porphyrin (83% versus ∼50%) with orders of magnitude enhancement in standard rate constant ( k s = 2.2 × 10 2 M −1 s −1 versus k s = 3 × 10 0 M −1 s −1 ). This work expands the use of coordination-driven self-assembly beyond ORR to water by exploiting post-synthetic modification and structural control that is associated with this synthetic method. 

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4. Fabrication and preliminary testing of patterned silver cathodes for proton conducting IT-SOFCs

   https://doi.org/10.1039/D3MA00793F  

   Sozal, Md Shariful ; Li, Wenhao ; Das, Suprabha ; Jafarizadeh, Borzooye ; Chowdhury, Azmal Huda ; Wang, Chunlei ; Cheng, Zhe ( January 2024 , Materials Advances)

   Dense silver (Ag) cathodes with defined triple phase boundary (TPB between the interface of electrolyte, electrode, and gas) lengths (LTPB) and electrode areas (AELT) were fabricated by photolithography and E-beam evaporation over a proton conducting BaZr0.4Ce0.4Y0.1Yb0.1O3−δ (BZCYYb4411) electrolyte. A bi-layer lift-off resist method appears to be more versatile than a single layer lift-off resist method for successful patterned cathode fabrication. The electrochemical behaviors of the patterned Ag cathodes over the BZCYYb4411 electrolyte were tested by electrochemical impedance spectroscopy (EIS) at different temperatures in atmospheres with different concentrations of O2 and H2O. The results were processed using Distribution of Relaxation Times (DRT) and reaction order analyses and also fitted to equivalent circuits. The directions for future work on patterned electrodes with different LTPB and AELT and theoretical calculations to gain further insights into the kinetics and mechanism of the cathode oxygen reduction reaction (ORR) over proton conducting electrolytes are pointed out. 

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5. Oxygen Reduction Electrocatalysis with Epitaxially Grown Spinel MnFe 2 O 4 and Fe 3 O 4

   https://doi.org/10.1021/acscatal.1c05172  

   Bredar, Alexandria R. ; Blanchet, Miles D. ; Burton, Andricus R. ; Matthews, Bethany E. ; Spurgeon, Steven R. ; Comes, Ryan B. ; Farnum, Byron H. ( March 2022 , ACS Catalysis)

   Nanocrystalline MnFe2O4 has shown promise as a catalyst for the oxygen reduction reaction (ORR) in alkaline solutions, but the material has been sparingly studied as highly ordered thin-film catalysts. To examine the role of surface termination and Mn and Fe site occupancy, epitaxial MnFe2O4 and Fe3O4 spinel oxide films were grown on (001)- and (111)-oriented Nb:SrTiO3 perovskite substrates using molecular beam epitaxy and studied as electrocatalysts for the oxygen reduction reaction (ORR). High-resolution X-ray diffraction (HRXRD) and X-ray photoelectron spectroscopy (XPS) show the synthesis of pure phase materials, while scanning transmission electron microscopy (STEM) and reflection high-energy electron diffraction (RHEED) analysis demonstrate island-like growth of (111) surface-terminated pyramids on both (001)- and (111)-oriented substrates, consistent with the literature and attributed to the lattice mismatch between the spinel films and the perovskite substrate. Cyclic voltammograms under a N2 atmosphere revealed distinct redox features for Mn and Fe surface termination based on comparison of MnFe2O4 and Fe3O4. Under an O2 atmosphere, electrocatalytic reduction of oxygen was observed at both Mn and Fe redox features; however, a diffusion-limited current was only achieved at potentials consistent with Fe reduction. This result contrasts with that of nanocrystalline MnFe2O4 reported in the literature where the diffusion-limited current is achieved with Mn-based catalysis. This difference is attributed to a low density of Mn surface termination, as determined by the integration of current from CVs collected under N2, in addition to low conductivity through the MnFe2O4 film due to the degree of inversion. Such low densities are attributed to the synthetic method and island-like growth pattern and highlight challenges in studying ORR catalysis with single-crystal spinel materials. 

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