RESUMEN
Dual atom catalysts, bridging single atom and metal/alloy nanoparticle catalysts, offer more opportunities to enhance the kinetics and multifunctional performance of oxygen reduction/evolution and hydrogen evolution reactions. However, the rational design of efficient multifunctional dual atom catalysts remains a blind area and is challenging. In this study, we achieved controllable regulation from Co nanoparticles to CoN4 single atoms to Co2N5 dual atoms using an atomization and sintering strategy via an N-stripping and thermal-migrating process. More importantly, this strategy could be extended to the fabrication of 22 distinct dual atom catalysts. In particular, the Co2N5 dual atom with tailored spin states could achieve ideally balanced adsorption/desorption of intermediates, thus realizing superior multifunctional activity. In addition, it endows Zn-air batteries with long-term stability for 800 h, allows water splitting to continuously operate for 1000 h, and can enable solar-powered water splitting systems with uninterrupted large-scale hydrogen production throughout day and night. This universal and scalable strategy provides opportunities for the controlled design of efficient multifunctional dual atom catalysts in energy conversion technologies.
RESUMEN
Developing efficient and affordable electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a significant barrier that needs to be overcome for the practical applications of hydrogen production via water electrolysis, transforming CO2 to value-added chemicals, and metal-air batteries. Recently, hydroxides have shown promise as electrocatalysts for OER. In situ or operando techniques are particularly indispensable for monitoring the key intermediates together with understanding the reaction process, which is extremely important for revealing the formation/OER catalytic mechanism of hydroxides and preparing cost-effective electrocatalysts for OER. However, there is a lack of comprehensive discussion on the current status and challenges of studying these mechanisms using in situ or operando techniques, which hinders our ability to identify and address the obstacles present in this field. This review offers an overview of in situ or operando techniques, outlining their capabilities, advantages, and disadvantages. Recent findings related to the formation mechanism and OER catalytic mechanism of hydroxides revealed by in situ or operando techniques are also discussed in detail. Additionally, some current challenges in this field are concluded and appropriate solution strategies are provided.
RESUMEN
Breakthrough in developing cost-effective Fe-based catalysts with superior oxygen reduction reaction (ORR) activities and ultra-long-term stability for application in Zn-air batteries (ZABs) remain a priority but still full of challenges. Herein, the neighboring NiN4 single-metal-atom and Fe2N5 dual-metal-atoms on the N-doped hollow carbon sphere (Fe/Ni-NHCS) were deliberately constructed as the efficient and robust ORR catalyst for ZABs. Both theory calculations and magnetic measurements demonstrate that the introduction of NiN4 provides a significant role on optimizing the electron spin state of Fe2N5 sites and reducing the energy barrier for the adsorption and conversion of the oxygen-containing intermediates, enabling the Fe/Ni-NHCS with excellent ORR performance and ultralow byproduct HO2- yield (0.5%). Impressively, the ZABs driven by Fe/Ni-NHCS exhibit unprecedented long-term rechargeable stability over 1200 h. This work paves a new venue to manipulate the spin state of active sites for simultaneously achieving superior catalytic activities and ultra-long-term stability in energy conversion technologies.
RESUMEN
Layered double hydroxides (LDHs), whose formation is strongly related to OH- concentration, have attracted significant interest in various fields. However, the effect of the real-time change of OH- concentration on LDHs' formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH3 gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi-LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported.
RESUMEN
Employing seawater splitting systems to generate hydrogen can be economically advantageous but still remains challenging, particularly for designing efficient and high Cl- -corrosion resistant trifunctional catalysts toward the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Herein, single CoNC catalysts with well-defined symmetric CoN4 sites are selected as atomic platforms for electronic structure tailoring. Density function theory reveals that P-doping into CoNC can lead to the formation of asymmetric CoN3 P1 sites with symmetry-breaking electronic structures, enabling the affinity of strong oxygen-containing intermediates, moderate H adsorption, and weak Cl- adsorption. Thus, ORR/OER/HER activities and stability are optimized simultaneously with high Cl- -corrosion resistance. The asymmetric CoN3 P1 structure based catalyst with boosted ORR/OER/HER performance endows seawater-based Zn-air batteries (S-ZABs) with superior long-term stability over 750 h and allows seawater splitting to operate continuously for 1000 h. A self-driven seawater splitting powered by S-ZABs gives ultrahigh H2 production rates of 497 µmol h-1 . This work is the first to advance the scientific understanding of the competitive adsorption mechanism between Cl- and reaction intermediates from the perspective of electronic structure, paving the way for synthesis of efficient trifunctional catalysts with high Cl- -corrosion resistance.
RESUMEN
Electrochemical reduction of O2 (oxygen reduction reaction; ORR) provides an opportunity to achieve the commercial application of clean energy, but it remains challenging, so the rational design of inexpensive and efficient electrocatalysts is required. Palladium-based electrocatalysts have emerged as a class of the most promising candidates for the ORR, which could accelerate O2 adsorption, dissociation, and electron transfer. However, the metal Pd atoms tend to aggregate into nanoparticles, driven by the tendency of the metal surface free energy to decrease, which significantly reduces the atom utilization efficiency and the catalytic performance. Herein, a facile double solvent impregnation method is developed for the synthesis of highly dispersed Pd nanoparticles supported on hollow carbon spheres (Pd-HCS), which could act as efficient electrocatalysts for the ORR in basic solution. Systematic investigation reveals that the nitrogen-containing and oxygen-containing functional groups (especially -COOH groups) are essential for achieving the homogenous dispersion of Pd nanoparticles. Significantly, the optimized Pd-HCS electrocatalyst with homogeneously dispersed Pd nanoparticles and Pd-N sites delivers high electrocatalytic activity for the ORR and excellent stability, without significant decay in onset potential and half-potential and good resistance to methanol crossover. This work offers a new route for the rational design of efficient ORR electrocatalysts toward advanced materials and emerging applications.
RESUMEN
Nonprecious-metal-based electrocatalysts with low cost, high activity, and stability are considered as one of the most promising alternatives to Pt-based catalysts for the oxygen reduction reaction (ORR). Herein, an economical and easy-to-fabricate catalyst is developed, that is, Fe/Fe3 C embedded in N-doped hollow carbon spheres (Fe/Fe3 C/NHCS), which gave the half-wave potential of 0.84â V in 0.1 m KOH, similar to the commercial Pt/C catalyst. Surprisingly, the favorable ORR performance of the as-prepared catalyst was obtained in both acidic and neutral conditions with almost a four-electron pathway and low H2 O2 yield, which desirable the development of the proton exchange membrane (PEM) and microbial electrolysis cell (MEC) technology. Additionally, the obtained catalyst demonstrated better long-term stability and high methanol tolerance over a wide range of pH. These features could be mainly attributed to the synergistic effect between Fe/Fe3 C and Fe-Nx sites, the hollow structure with mesopores, and the well-dispersed Fe/Fe3 C nanoparticles owing to the existence of the abundant hydrophilic groups within the HCS precursor. As such, designing an efficient and cheap ORR catalyst that can operate at alkaline, acidic, and neutral solutions is highly desirable, yet challenging.