Electrochemical carbon monoxide reduction is a promising strategy for the production of value-added multicarbon compounds, albeit yielding diverse products with low selectivities and Faradaic efficiencies. Here, copper single atoms anchored to Ti3C2Tx MXene nanosheets are firstly demonstrated as effective and robust catalysts for electrochemical carbon monoxide reduction, achieving an ultrahigh selectivity of 98% for the formation of multicarbon products. Particularly, it exhibits a high Faradaic efficiency of 71% towards ethylene at −0.7 V versus the reversible hydrogen electrode, superior to the previously reported copper-based catalysts. Besides, it shows a stable activity during the 68-h electrolysis. Theoretical simulations reveal that atomically dispersed Cu–O3 sites favor the C–C coupling of carbon monoxide molecules to generate the key *CO-CHO species, and then induce the decreased free energy barrier of the potential-determining step, thus accounting for the high activity and selectivity of copper single atoms for carbon monoxide reduction.
The ambient electrocatalytic N2 reduction reaction (NRR) is a promising alternative to the Haber–Bosch process for producing NH3. However, a guideless search for single-atom-based and other electrocatalysts cannot promote the NH3 yield rates by NRR efficiently. Herein, our first-principles calculations reveal that the successive emergence of vertical end-on *N2 and oblique end-on *NNH admolecules on single metal sites is key to high-performance NRR. By targeting the admolecules, single Ag sites with the Ag–N4 coordination are found and synthesized massively. They exhibit a record-high NH3 yield rate (270.9 μg h–1 mgcat. –1 or 69.4 mg h–1 mgAg –1) and a desirable Faradaic efficiency (21.9%) in HCl aqueous solution under ambient conditions. The generation rate of NH3 is stable during 20 consecutive reaction cycles, and the reduction current density is almost constant for 60 h. This work provides an effective targeting-design principle to purposefully synthesize active and durable single-atom-based NRR electrocatalysts.
Ceramic aerogels are attractive candidates for high-temperature thermal insulation, catalysis support, and ultrafiltration materials, but their practical applications are usually limited by brittleness. Recently, reversible compressibility has been realized in flexible nanostructures-based ceramic aerogels. However, these modified aerogels still show fast and brittle fracture under tension. Herein, we demonstrate achieving reversible stretch and crack insensitivity in a highly compressible ceramic aerogel through engineering its microstructure by using curly SiC-SiO x bicrystal nanowire as the building blocks. The aerogel exhibits large-strain reversible stretch (20%) and good resistance to high-speed tensile fatigue test. Even for a prenotched sample, a reversible stretch at 10% strain is achieved, indicating good crack resistance. The aerogel also displays reversible compressibility up to 80% strain, ultralow thermal conductivity of 28.4 mW m–1 K–1, and excellent thermal stability even at temperatures as high as 1200 °C in butane blow torch or as low as −196 °C in liquid nitrogen. Our findings show that the attractive tensile properties arise from the deformation, interaction, and reorientation of the curly nanowires which could reduce stress concentration and suppress crack initiation and growth during tension. This study not only expands the applicability of ceramic aerogels to conditions involving complex dynamic stress under extreme temperature conditions but also benefits the design of other highly stretchable and crack-resistant porous ceramic materials for various applications.
The CO2 reduction reaction (CO2RR) driven by renewable electricity represents a promising strategy toward alleviating the energy shortage and environmental crisis facing humankind. Cu species, as one type of versatile electrocatalyst for the CO2RR, attract tremendous research interest. However, for C2 products, ethanol formation is commonly less favored over Cu electrocatalysts. Herein, AuCu alloy nanoparticle embedded Cu submicrocone arrays (AuCu/Cu‐SCA) are constructed as an active, selective, and robust electrocatalyst for the CO2RR. Enhanced selectivity for EtOH is gained, whose Faradaic efficiency (FE) reaches 29 ± 4%, while ethylene formation is relatively inhibited (16 ± 4%) in KHCO3 aqueous solution. The ratio between partial current densities of EtOH and C2H4 (jEtOH/jC2H4) can be tuned in the range from 0.15 ± 0.27 to 1.81 ± 0.55 by varying the Au content of the electrocatalysts. The combined experimental and theoretical calculation results identify the importance of Au in modifying binding energies of key intermediates, such as CH2CHO*, CH3CHO*, and CH3CH2O*, which consequently modify the activity and selectivity (jEtOH/jC2H4) for the CO2RR. Moreover, AuCu/Cu‐SCA also shows high durability with both the current density and FEEtOH being largely maintained for 24 h electrocatalysis.
The fabrication of Zn‐CO2 batteries is a promising technique for CO2 fixation and energy storage. Herein, nitrogen‐doped ordered mesoporous carbon (NOMC) is adopted as a bifunctional metal‐free electrocatalyst for CO2 reduction and oxygen evolution reaction in the near‐neutral electrolyte. The ordered mesoporous structures and abundant N‐dopings of NOMC facilitate the accessibility and utilization of the active sites, which endow NOMC with excellent electrocatalysis performance and outstanding stability. Especially, a nearly 100% CO Faradaic efficiency is achieved at an ultralow overpotential of 360 mV for CO2 reduction. When constructed as an aqueous rechargeable Zn‐CO2 battery using NOMC as the cathode, it yields a high peak power density of 0.71 mW cm−2, a good cyclability of 300 cycles, and excellent energy efficiency of 52.8% at 1.0 mA cm−2.
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