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1. Carbon aerogels with atomic dispersion of binary iron–cobalt sites as effective oxygen catalysts for flexible zinc–air batteries

   https://doi.org/10.1039/d0ta04633g  

   Chen, Yang ; Hu, Shengqiang ; Nichols, Forrest ; Bridges, Frank ; Kan, Shuting ; He, Ting ; Zhang, Yi ; Chen, Shaowei ( June 2020 , Journal of Materials Chemistry A)

   null (Ed.)

   Iron single atom catalysts have emerged as one of the most active electrocatalysts towards the oxygen reduction reaction (ORR), but the unsatisfactory durability and limited activity for the oxygen evolution reaction (OER) has hampered their commercial applications in rechargeable metal–air batteries. By contrast, cobalt-based catalysts are known to afford excellent ORR stability and OER activity, due to the weak Fenton reaction and low OER Gibbs free energy. Herein, a bimetal hydrogel template is used to prepare carbon aerogels containing Fe–Co bimetal sites (NCAG/Fe–Co) as bifunctional electrocatalysts towards both ORR and OER, with enhanced activity and stability, as compared to the monometal counterparts. High-resolution transmission electron microscopy, elemental mapping and X-ray photoelectron spectroscopy measurements demonstrate homogeneous distributions of the metal centers within defected carbon lattices by coordination to nitrogen dopants. X-ray absorption spectroscopic measurements, in combination with other results, suggest the formation of FeN 3 and CoN 3 moieties on mutually orthogonal planes with a direct Fe–Co bonding interaction. Electrochemical measurements show that NCAG/Fe–Co delivers a small ORR/OER potential gap of only 0.64 V at the current density of 10 mA cm −2 , 60 mV lower than that (0.70 V) with commercial Pt/C and RuO 2 catalysts. When applied in a flexible Zn–air battery, the dual-metal NCAG/Fe–Co catalyst also shows a remarkable performance, with a high open-circuit voltage of 1.47 V, a maximum power density of 117 mW cm −2 , as well as good rechargeability and flexibility. Results from this study may offer an ingenious protocol in the design and engineering of highly efficient and durable bifunctional electrocatalysts based on dual metal-doped carbons. 

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2. Single iron atoms stabilized by microporous defects of biomass-derived carbon aerogels as high-performance cathode electrocatalysts for aluminum–air batteries

   https://doi.org/10.1039/c9ta05981d  

   He, Ting ; Zhang, Yaqian ; Chen, Yang ; Zhang, Zhenzhu ; Wang, Haiyan ; Hu, Yongfeng ; Liu, Min ; Pao, Chih-Wen ; Chen, Jeng-Lung ; Chang, Lo Yueh ; et al ( September 2019 , Journal of Materials Chemistry A)

   Atomically dispersed metal catalysts have demonstrated superb electrocatalytic activity because of optimal atom efficiency. However, a rational design of low-cost, high-performance single atom catalysts remains a great challenge due to the elusive chemical reactions of the formation of metal active sites. In this work, biomass hydrogel is prepared as a template for mass production of three-dimensional carbon aerogel-supported single metal atom catalysts. By tailoring the structure of the hydrogel templates, the obtained carbon aerogels exhibit an increase of microporous defects which capture and stabilize isolated metal atoms and minimize aggregation during pyrolysis. Extended X-ray absorption fine structure, Mössbauer spectroscopy, and nitrogen adsorption–desorption isotherm measurements indicate that single metal centers of FeN 4 are formed and embedded within the hierarchical porous carbon frameworks. The obtained composites exhibit outstanding catalytic activity towards oxygen reduction in alkaline media, with a high onset potential of +1.05 V and half-wave potential of +0.88 V, as well as excellent durability. Remarkably, when the carbon aerogels are used as the cathode catalyst in an aluminum–air battery, the battery achieves an ultrahigh open-circuit voltage of 1.81 V, large power density of 181.1 mW cm −2 and stable discharge voltage of 1.70 V at 20 mA cm −2 , markedly better than those with commercial Pt/C as the cathode catalyst. 

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3. Template-assisted synthesis of ultrathin graphene aerogels as bifunctional oxygen electrocatalysts for water splitting and alkaline/neutral zinc-air batteries

   https://doi.org/10.1016/j.cej.2023.141492  

   Li, Qiang ; Sun, Zhifang ; Yin, Chunyang ; Chen, Yang ; Pan, Dingjie ; Yu, Bingzhe ; Zhang, Yi ; He, Ting ; Chen, Shaowei ( February 2023 , Chemical Engineering Journal)

   Low-cost, high-performance oxygen catalysts are critical for electrochemical water splitting and metal-air batteries. Herein, carbon aerogels with skeletons consisting of few-layer graphene are derived pyrolytically from a hydrogel precursor using an array of NaCl crystals as the template, exhibiting a high electrical conductivity (869 S m−1) and an ultralow mass density (11.1 mg cm−3). The deposition of NiFe layered double hydroxide (NiFeLDH) nanocolloids renders the aerogels active towards both the oxygen reduction/evolution reactions (ORR/OER), with the performances highly comparable to those of commercial benchmarks in both alkaline and neutral media. Results from operando Raman spectroscopy measurements and first principles calculations suggest that Fe(OH)3 colloids facilitate the oxidation of Ni2+, which lowers the energy barrier to 0.42 eV for OER, whereas the nitrogen-doped carbon aerogels are responsible for the ORR activity. With the composites used as bifunctional oxygen catalysts for electrochemical water splitting and rechargeable zinc-air batteries, the performances in both alkaline and neutral media are markedly better than those based on the mixture of commercial Pt/C and RuO2. Results from this study highlight the unique advantages of ultrathin graphene aerogels in the development of effective catalysts for electrochemical energy devices. 

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4. 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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5. 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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