Molecular Design of Single‐Atom Catalysts for Oxygen Reduction Reaction

Fuel cells are highly attractive for direct chemical‐to‐electrical energy conversion and represent the ultimate mobile power supply solution. However, presently, fuel cells are limited by the sluggish kinetics of the cathodic oxygen reduction reaction (ORR), which requires the use of Pt as a catalyst, thus significantly increasing the overall cost of the cells. Recently, nonprecious metal single‐atom catalysts (SACs) with high ORR activity under both acidic and alkaline conditions have been recognized as promising cost‐effective alternatives to replace Pt in fuel cells. Considerable efforts have been devoted to further improving the ORR activity of SACs, including tailoring the coordination structure of the metal centers, enriching the concentration of the metal centers, and engineering the electronic structure and porosity of the substrate. Herein, a brief introduction to fuel cells and fundamentals of the ORR parameters of SACs and the origin of their high activity is provided, followed by a detailed review of the recently developed strategies used to optimize the ORR activity of SACs in both rotating disk electrode and membrane electrode assembly tests. Remarks and perspectives on the remaining challenges and future directions of SACs for the development of commercial fuel cells are also presented.     

Spontaneous Atomic Ruthenium Doping in Mo2CTX MXene Defects Enhances Electrocatalytic Activity for the Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) process usually suffers extremely low Faradaic efficiency and ammonia yields due to sluggish N?N dissociation. Herein, single‐atomic ruthenium modified Mo₂CT_X MXene nanosheets as an efficient electrocatalyst for nitrogen fixation at ambient conditions are reported. The catalyst achieves a Faradaic efficiency of 25.77% and ammonia yield rate of 40.57 µg h^?1 mg^?1 at ‐0.3 V versus the reversible hydrogen electrode in 0.5 m K₂SO₄ solution. Operando X‐ray absorption spectroscopy studies and density functional theory calculations reveal that single‐atomic Ru anchored on MXene nanosheets act as important electron back‐donation centers for N₂ activation, which can not only promote nitrogen adsorption and activation behavior of the catalyst, but also lower the thermodynamic energy barrier of the first hydrogenation step. This work opens up a promising avenue to manipulate catalytic performance of electrocatalysts utilizing an atomic‐level engineering strategy.     

Highly Efficient and Durable Pd Hydride Nanocubes Embedded in 2D Amorphous NiB Nanosheets for Oxygen Reduction Reaction

A highly efficient and durable electrocatalyst of Pd hydride nanocubes encapsulated within 2D amorphous Ni‐B nanosheets is reported. The PdH_0.43 nanocubes are first synthesized via a simple N ,N ‐dimethylformamide thermal treatment. The as‐synthesized PdH_0.43 nanocubes are then encapsulated in 2D amorphous NiB nanosheets by NaBH₄ reduction in the presence of nickel species. During the NaBH₄ treatment, the PdH_0.43 can be further transformed into PdH_0.706 due to the presence of endogenous H₂. Electrochemical studies demonstrate that the degree of hydride of Pd nanocubes (PdH_x ) plays an important role in the enhancement of their oxygen reduction reaction (ORR) activity. With increasing x value, both the activity and stability increase significantly. At 0.90 V versus reversible hydrogen electrode, the ORR activity of PdH_0.706 @Ni‐B reaches 1.05 A mg_Pd^?1, which is nearly five times higher than that of the state‐of‐the‐art Pt catalysts. Accelerated durability tests show that even after 10 000 potential cycles, there is negligible shift in their half‐wave potential and no shape and structure change occurs, indicating the incorporation of amorphous 2D Ni‐B nanosheets can greatly improve their stability without compromising their activity. The present study illustrates the importance of high degree of hydride and presence of amorphous Ni‐B nanosheets on the enhancement of ORR activity for Pd‐based electrocatalyst.     

Oxygen Reduction Reaction Affected by Sulfate-Reducing Bacteria: Different Roles of Bacterial Cells and Metabolites

Sulfate-reducing bacteria (SRB) were found to be capable of tolerating a certain amount of oxygen (O₂), but how they affect oxygen reduction reaction (ORR) has not been clear. The present work investigated the impact of SRB on ORR in 3.5 wt% sodium chloride solution with the cyclic voltammetry method. The addition of SRB culture solution hampered both the reduction of O₂ to superoxide (O ₂ ^·? ) and hydrogen peroxide (H₂O₂) to water (H₂O), and the influence of SRB metabolites was much larger than that of bacterial cells. Sulfide and extracellular polymeric substances (EPS), typical inorganic and organic metabolic products, had great impact on ORR. Sulfide played an important role in the decrease of cathodic current for H₂O₂ reduction due to its hydrolysis and chemical reaction activity with H₂O₂. EPS were sticky, easy to adsorb on the electrode surface and abundant in functional groups, which hindered the transformation of O₂ into O ₂ ^·? and favored the reduction of H₂O₂ to H₂O.     

Harmonized Physical and Electrochemical Process Design for Densely Dispersed Cu Catalysts on Cu2O Absorbers for Efficient Photoelectrochemical CO2 Reduction Reaction

The photoelectrochemical CO₂ reduction reaction (photo-CO₂RR) is a promising technology to convert CO₂ into high-value-added carbon-based chemicals using a relatively low voltage, which can economically solve the problem of CO₂ emissions. Nevertheless, unlike the conventional electrochemical CO₂RR approach, photo-CO₂RR technology is in its initial development stage. Particularly, when sunlight is applied to photoelectrodes for photo-CO₂RR, severe photocorrosion is unavoidable, resulting in the deterioration of fundamental functions including device long-term stability and conversion performance. This study proposes an innovative two-step catalyst formation strategy to enable the efficient photo-CO₂RR with Cu catalysts prepared using intrinsic photocorrosion of the Cu₂O absorption layer. This approach is based on the harmonized process design of the i) growth of physically generated Cu nanoparticles and ii) construction of improved photoelectrochemical Cu cluster catalysts. The vacuum-evaporated Cu seeds are designed to induce an evenly dispersed electrical path on Cu₂O, and the selectively concentrated electrical field from the Cu seeds provides preferential sites for metallic Cu catalysts in subsequent photoelectrochemical reduction. This harmonized combination process of Cu catalysts on Cu₂O demonstrates a synergistic performance of −1.2 mA cm⁻² at 0 V_RHE with suppression of photocorrosion and produces ≈95% CO product gas (0.4 V_RHE).     

Post Iron Decoration of Mesoporous Nitrogen‐Doped Carbon Spheres for Efficient Electrochemical Oxygen Reduction

Iron–nitrogen–carbon (Fe–N–C) catalysts are considered as the most promising nonprecious metal catalysts for oxygen reduction reactions (ORRs). Their synthesis generally involves complex pyrolysis reactions at high temperature, making it difficult to optimize their composition, pore structure, and active sites. This study reports a simple synthesis strategy by reacting preformed nitrogen‐doped carbon scaffolds with iron pentacarbonyl, a liquid precursor that can effectively form active sites with the nitrogen sites, enabling more effective control of the catalyst. The resultant catalyst possesses a well‐defined mesoporous structure, a high surface area, and optimized active sites. The catalysts exhibit high ORR activity comparable to that of Pt/C catalyst (40% Pt loading) in alkaline media, with excellent stability and methanol tolerance. The synthetic strategy can be extended to synthesize other metal–N–C catalysts.     

Ultrathin YSZ Coating on Pt Cathode for High Thermal Stability and Enhanced Oxygen Reduction Reaction Activity

A simple, yet effective approach of stabilizing the nanostructure of porous metal‐based electrodes and thus, extending the life of microsolid oxide fuel cells is demonstrated. In an effort to avoid thermal agglomeration of metal electrodes, an ultrathin yttria‐stabilized zirconia (YSZ) is coated on the porous metal (Pt) cathode by the atomic layer deposition, a scalable, and potentially high‐throughput deposition technique. A very thin YSZ coating is found to maintain the morphology of its underlying nanoporous Pt during high temperature operations (500 °C). More interestingly, the YSZ coating is also found to improve oxygen reduction reaction activity by ≈2.5 times. This improvement is attributed to an enhanced triple phase area, especially in the vicinity of the Pt–electrolyte interface; cross‐sectional electron microscopy images indicate that the initially uniform ultrathin YSZ layer becomes a partially agglomerated coating, a favorable structure for a maximized reaction area and fluent oxygen access to the Pt–electrolyte interface.     

Hydrogen Effect on Nitrogenase (C2H2 Reduction) Response to Oxygen in Bradyrhizobium japonicum-Phaseoleae Symbioses

The influence of hydrogenase in Bradyrizobum-Phaseoleae symbioseswas studied ex-planta and in-planra in soybean (Glycine max)and cowpea (Vigna unguiculata). The hydrogenase was activatedby the addition of hydrogen in the incubation gas phase whichmodified the response of nitrogenase activity of Hup⁺ (hydrogenuptake positive) symbiosis to the external oxygen partial pressure.For bacteroids the hydrogenase expression increased nitrogenaseactivity at supraoptimal pO₂, acting possibly as a respiratoryprotection of nitrogenase. However, at suboptimal pO₂, nitrogenaseactivity of Hup⁺ bacteroids decreased with hydrogen, a phenomenonattributed to the lower efficiency of ATP synthesis from hydrogenthan from carbon substrates oxidation. For undisturbed nodules,the hydrogenase expression in soybean increased the optimalpO₂ for ARA (COP), from 35.3 to 40.3 kPa O₂, and the ARA atsupraoptimal pO₂; at suboptimal PO₂ there was a negative effectof hydrogenase on ARA, although this inhibition was less thanon bacteroids and was not detected if plants were grown at 15°C rather than 20 °C root temperature. No H₂ effectwas detected on cowpea nodules. The results on soybean nodulesare consistent with the concept that symbiotic nitrogen fixationis oxygen-limited and that hydrogenase activity has no beneficialeffect on nitrogen fixation in O₂ limitation. Key words: Glycine max, hydrogenase, nitrogenase, nitrogen fixation, nodules, Vigna unguiculata     

Structurally Ordered Fe3Pt Nanoparticles on Robust Nitride Support as a High Performance Catalyst for the Oxygen Reduction Reaction

The commercialization of fuel cell technologies requires a significant reduction in the amount of expensive platinum catalyst in the cathode while still maintaining high catalytic activity and stability. Herein a cost‐effective, highly durable, and efficient catalyst consisting of ordered Fe₃Pt nanoparticles supported by mesoporous Ti_0.5Cr_0.5N (Fe₃Pt/Ti_0.5Cr_0.5N) is demonstrated. The Fe₃Pt/Ti_0.5Cr_0.5N catalyst exhibits a five‐fold increase in mass activity relative to a Pt/C catalyst at 0.9 V for the oxygen reduction reaction. More importantly, the catalyst shows a minimal loss of activity after 5000 potential cycles (9.7%). The enhanced activity of the ordered Fe₃Pt/Ti_0.5Cr_0.5N catalyst, in combination with its enhanced stability, makes it very promising for the development of new cathode catalysts for fuel cells.     

Active MnOx Electrocatalysts Prepared by Atomic Layer Deposition for Oxygen Evolution and Oxygen Reduction Reactions

The ability to deposit conformal catalytic thin films enables opportunities to achieve complex nanostructured designs for catalysis. Atomic layer deposition (ALD) is capable of creating conformal thin films over complex substrates. Here, ALD‐MnO_x on glassy carbon is investigated as a catalyst for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), two reactions that are of growing interest due to their many applications in alternative energy technologies. The films are characterized by X‐ray photoelectron spectroscopy, X‐ray diffraction, scanning electron microscopy, ellipsometry, and cyclic voltammetry. The as‐deposited films consist of Mn(II)O, which is shown to be a poor catalyst for the ORR, but highly active for the OER. By controllably annealing the samples, Mn₂O₃ catalysts with good activity for both the ORR and OER are synthesized. Hypotheses are presented to explain the large difference in the activity between the MnO and Mn₂O₃ catalysts for the ORR, but similar activity for the OER, including the effects of surface oxidation under experimental conditions. These catalysts synthesized though ALD compare favorably to the best MnO_x catalysts in the literature, demonstrating a viable way to produce highly active, conformal thin films from earth‐abundant materials for the ORR and the OER.     

Selective Etching of Nitrogen‐Doped Carbon by Steam for Enhanced Electrochemical CO2 Reduction

Nitrogen‐doped carbon structures have recently been demonstrated as a promising candidate for electrocatalytic CO₂ reduction, while in the meantime the pyridinic and graphitic nitrogen atoms also present high activities for electroreduction of water. Here, an etching strategy that uses hot water steam to preferentially bind to pyridinic and graphitic nitrogen atoms and subsequently etch them in carbon frameworks is reported. As a result, pyrrolic nitrogen atoms with low water affinity are retained after the steam etching, with a much increased level of among all nitrogen species from 22.1 to 55.9%. The steam‐etched nitrogen‐doped carbon catalyst enables excellent electrocatalytic CO₂ reduction performance but low hydrogen evolution reaction activity, suggesting a new approach for tuning electrocatalyst activity.     

Photocatalytic Reduction of CO2 into Methanol over Ag/TiO2 Nanocomposites Enhanced by Surface Plasmon Resonance

Ag-loaded TiO₂ (Ag/TiO₂) nanocomposites were prepared by microwave-assisted chemical reduction method using tetrabutyl titanate as the Ti source. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N₂ adsorption–desorption isotherms, UV–vis absorption spectrum, X-ray photoelectron spectrum, photoluminescence spectrum, and Raman scattering spectrum, respectively. Results revealed that Ag nanoparticles (NPs) were successfully deposited on TiO₂ by reduction of Ag⁺, and the visible light absorption and Raman scattering of TiO₂ were enhanced by Ag NPs based on its surface plasmon resonance effect. Besides, Ag NPs could also effectively restrain the recombination of photogenerated electrons and holes with a longer luminescence life time. In addition, photocatalytic reduction of CO₂ with H₂O on the composites was conducted to obtain methanol. Experimental results indicated that Ag-loaded TiO₂ had better photocatalytic activity than pure TiO₂ due to the synergistic effect between UV light excitation and surface plasmon resonance enhancement, and 2.5 % Ag/TiO₂ exhibited the best activity; the corresponding energy efficiency was about 0.5 % and methanol yield was 405.2 μmol/g-cat, which was 9.4 times higher than that of pure TiO₂. Additionally, an excitation enhancement synergistic mechanism was proposed to explain the experimental results of photocatalytic reduction of CO₂ under different reaction conditions.     

Reduction of Mercury to the Elemental State by a Yeast

A yeast of the genus Cryptococcus has been isolated from a stream and was shown to be capable of reducing mercury to the elemental state. The organism grows in Wickerham broth supplemented with high concentrations of mercury (II) chloride (180 mg of mercury per liter) and will metabolize [(14)C]glucose in this medium as do cells in the absence of mercury. Mercury was associated with the cell wall and membrane, and in vacuoles within the cytoplasm.     

Degradation Mechanism and Enhancing Strategies of Oxygen Reduction Reaction Catalyzed by Carbon-Based Metal Free Catalysts in Acidic Solution

Carbon-based metal free catalysts (CMFCs) are far away from commercial availability mainly attributed to their poor oxygen reduction reaction (ORR) performance in acidic environment with the causes remaining obscure. By investigating the heteroatoms (N, B, P, S, Se, and Te)-doped reduced graphene oxides, the degradation mechanism of acidic ORR performance of CMFCs is found to be correlated with the oxygen-baring defects in the carbon sp² lattice, which exhibit overpotentials as low as 0.44 V but weak trapping capabilities for oxygen molecules. These findings not only revise the previously reported strategy of modeling the active sites in the basal plane of CMFCs but also highlight the connections between those active sites and the triple-coordinated VIA group elements (XC₃). Further calculations demonstrate that the XC₃ dimer can efficiently enhance the acidic ORR performance and the 2D trigonal carbon-chalcogenides C₆X (X = S, Se, and Te) are accordingly designed toward acidic ORR, which contain homogeneously distributed basal plane active sites and exhibit low overpotentials but strong trapping capabilities for oxygen molecules. This work will help to cease the debates on the active sites in CMFCs for ORR in both acidic and alkaline solutions and to open a new avenue to design CMFCs independent on doping strategy.     

Ultrathin Bilayer of Graphite/SiO2 as Solid Interface for Reviving Li Metal Anode

Lithium metal anodes are expected to drive practical applications that require high energy‐density storage. However, the direct use of metallic lithium causes safety concerns, low rate capabilities, and poor cycling performance due to unstable solid electrolyte interphase (SEI) and undesired lithium dendrite growth. To address these issues, a radio frequency sputtered graphite‐SiO₂ ultrathin bilayer on a Li metal chips is demonstrated, for the first time, as an effective SEI layer. This leads to a dendrite free uniform Li deposition to achieve a stable voltage profile and outstanding long hours plating/stripping compared to the bare Li. Compared to a bare Li anode, the graphite‐SiO₂ bilayer modified Li anode coupled with lithium nickel cobalt manganese oxide cathode (NMC111) and lithium titanate shows improved capacity retention, higher capacity at higher rates, longer cycling stability, and lower voltage hysteresis. Graphite acts as an electrical bridge between the plated Li and Li electrode, which lowers the impedance and buffers the volume expansion during Li plating/stripping. Adding an ultrathin SiO₂ layer facilitates Li‐ion diffusion and lithiation/delithiation, provides higher electrolyte affinity, higher chemical stability, and higher Young's modulus to suppress the Li dendrite growth.     

Metal‐Organic Framework‐Derived Non‐Precious Metal Nanocatalysts for Oxygen Reduction Reaction

By virtue of diverse structures and tunable properties, metal‐organic frameworks (MOFs) have presented extensive applications including gas capture, energy storage, and catalysis. Recently, synthesis of MOFs and their derived nanomaterials provide an opportunity to obtain competent oxygen reduction reaction (ORR) electrocatalysts due to their large surface area, controllable composition and pore structure. This review starts with the introduction of MOFs and current challenges of ORR, followed by the discussion of MOF‐based non‐precious metal nanocatalysts (metal‐free and metal/metal oxide‐based carbonaceous materials) and their application in ORR electrocatalysis. Current issues in MOF‐derived ORR catalysts and some corresponding strategies in terms of composition and morphology to enhance their electrocatalytic performance are highlighted. In the last section, a perspective for future development of MOFs and their derivatives as catalysts for ORR is discussed.