ABSTRACT
Interstitial filling of light atoms strongly affects the electronic structure and adsorption properties of the parent catalyst due to ligand and ensemble effects. Different from the conventional doping and surface modification, constructing ordered intermetallic structures is more promising to overcome the dissolution and reconstruction of active sites through strong interactions generated by atomic periodic arrangement, achieving joint improvement in catalytic activity and stability. However, for tightly arranged metal lattices, such as iridium (Ir), obtaining ordered filling atoms and further unveiling their interstitial effects are still limited by highly activated processes. Herein, we report a high-temperature molten salt assisted strategy to form the intermetallic Ir-B compounds (IrB1.1) with ordered filling by light boron (B) atoms. The B residing in the interstitial lattice of Ir constitutes favorable adsorption surfaces through a donor-acceptor architecture, which has an optimal free energy uphill in rate-determining step (RDS) of oxygen evolution reaction (OER), resulting in enhanced activity. Meanwhile, the strong coupling of Ir-B structural units suppresses the demetallation and reconstruction behavior of Ir, ensuring catalytic stability. Such B-induced interstitial effects endow IrB1.1 with higher OER performance than commercial IrO2, which is further validated in proton exchange membrane water electrolyzers (PEMWEs).
ABSTRACT
Electrocatalysis is a very attractive way to achieve a sustainable carbon cycle by converting CO2 into organic fuels and feedstocks. Therefore, it is crucial to design advanced electrocatalysts by understanding the reaction mechanism of electrochemical CO2 reduction reaction (eCO2RR) with multiple electron transfers. Among electrocatalysts, dual-atom catalysts (DACs) are promising candidates due to their distinct electronic structures and extremely high atomic utilization efficiency. Herein, the eCO2RR mechanism and the identification of intermediates using advanced characterization techniques, with a particular focus on regulating the critical intermediates are systematically summarized. Further, the insightful understanding of the functionality of DACs originates from the variable metrics of electronic structures including orbital structure, charge distribution, and electron spin state, which influences the active sites and critical intermediates in eCO2RR processes. Based on the intrinsic relationship between variable metrics and critical intermediates, the optimized strategies of DACs are summarized containing the participation of synergistic atoms, engineering of the atomic coordination environment, regulation of the diversity of central metal atoms, and modulation of metal-support interaction. Finally, the challenges and future opportunities of atomically dispersed catalysts for eCO2RR processes are discussed.
ABSTRACT
Ru-related catalysts have shown excellent performance for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR); however, a deep understanding of Ru-active sites on a nanoscale heterogeneous support for hydrogen catalysis is still lacking. Herein, a click chemistry strategy is proposed to design Ru cluster-decorated nanometer RuxFe3-xO4 heterointerfaces (Ru/RuxFe3-xO4) as highly effective bifunctional hydrogen catalysts. It is found that introducing Ru into nanometric Fe3O4 species breaks the symmetry configuration and optimizes the active site in Ru/RuxFe3-xO4 for HER and HOR. As expected, the catalyst displays prominent alkaline HER and HOR performance with mass activity much higher than that of commercial Pt/C as well as robust stability during catalysis because of the strong interaction between the Ru cluster and the RuxFe3-xO4 support, and the optimized adsorption intermediate (Had and OHad). This work sheds light on a promsing approach to improving the electrocatalysis performance of catalysts by the breaking of atomic dimension symmetry.
ABSTRACT
Efficient dual-single-atom catalysts are crucial for enhancing atomic efficiency and promoting the commercialization of fuel cells, but addressing the sluggish kinetics of hydrogen oxidation reaction (HOR) in alkaline media and the facile dual-single-atom site generation remains formidable challenges. Here, we break the local symmetry of ultra-small ruthenium (Ru) nanoparticles by embedding cobalt (Co) single atoms, which results in the release of Ru single atoms from Ru nanoparticles on reduced graphene oxide (Co1 Ru1,n /rGO). In situ operando spectroscopy and theoretical calculations reveal that the oxygen-affine Co atom disrupts the symmetry of ultra-small Ru nanoparticles, resulting in parasitic Ru and Co dual-single-atom within Ru nanoparticles. The interaction between Ru single atoms and nanoparticles forms effective active centers. The parasitism of Co atoms modulates the adsorption of OH intermediates on Ru active sites, accelerating HOR kinetics through faster formation of *H2 O. As anticipated, Co1 Ru1,n /rGO exhibits ultrahigh mass activity (7.68â A mgRu -1 ) at 50â mV and exchange current density (0.68â mA cm-2 ), which are 6 and 7 times higher than those of Ru/rGO, respectively. Notably, it also displays exceptional durability surpassing that of commercial Pt catalysts. This investigation provides valuable insights into hybrid multi-single-atom and metal nanoparticle catalysis.
ABSTRACT
The coordination environment of Ru centers determines their catalytic performance, however, much less attention is focused on cluster-induced charge transfer in a Ru single-atom system. Herein, by density functional theory (DFT) calculations, a competitive coordination-pairing between Ru clusters (RuRu bond) and single-atoms (RuO bond) is revealed leading to the charge redistribution between Ru and O atoms in ZnFe2 O4 units which share more free electrons to participate in the hydrogen desorption process, optimizing the proton adsorption and hydrogen desorption. Thus, a clicking confinement strategy for building a competitive coordination-pairing between Ru clusters and single-atoms anchored on ZnFe2 Ox nanosheets over carbon via RuO ligand (Ru1, n -ZnFe2 Ox -C) is proposed. Benefiting from the optimized coordination effect and the electronic synergy between Ru clusters and single-atoms, such a catalyst demonstrates the excellent activity and excellent stability in alkaline and seawater media, which has exceptional hydrogen evolution reaction activity with overpotentials as low as 10.1 and 15.9 mV to reach the current density of 10 mA cm-2 in alkaline and seawater media, respectively, higher than that of commercial Pt/C catalysts as a benchmark. Furthermore, it owns remarkably outstanding mass activity, approximately 2 and 8 times higher than that of Pt catalysts in alkaline and seawater media, respectively.
ABSTRACT
The density functional theory calculation results reveal that the adjacent defect concentration and electronic spin state can effectively activate the CoIII sites in the atomically thin nanosheets, facilitating the thermodynamic transformation of *O to *OOH, thus offering ultrahigh charge transfer properties and efficiently stabilizing the phase. This undoubtedly evidences that, for metal sulfides, the atom-scale cation/anion vacancy pair and surface electronic spin state can play a great role in enhancing the oxygen evolution reaction. Inspired by the theoretical prediction, interconnected selenium (Se) wired ultrathin Co3 S4 (Sex -Co3 S4 ) nanosheets with Co/S (Se) dual-vacancies (Se1.0 -Co3 S4 -VS/Se -VCo ) pairs are constructed by a simple approach. As an efficient sulfur host material, in an ultralow-concentration KOH solution (0.1 m), Se1.0 -Co3 S4 -VS/Se -VCo presents outstanding durability up to 165 h and a low overpotential of 289.5 mV at 10 mA cm-2 , which outperform the commercial Co3 S4 nanosheets (NSs) and RuO2 . Moreover, the turnover frequency of Se1.0 -Co3 S4 -VS/Se -VCo is 0.00965 s-1 at an overpotential of 0.39 V, which is 5.7 times that of Co3 S4 NSs, and 5.8 times that of commercial RuO2 . The finding offers a rational design strategy to create the multi-defect structure in catalysts toward high-efficiency water electrolysis.
Subject(s)
Selenium , Water , Cations , Oxidation-Reduction , OxygenABSTRACT
Electrocatalysis of the hydrogen evolution reaction (HER) is a vital and demanding, yet challenging, task to produce clean energy applications. Here, the RuRh2 bimetallene nanoring with rich structural defects is designed and successfully synthesized by a mixed-solvent strategy, displaying ascendant HER performance with high mass activity at -0.05 and -0.07 V, separately higher than that of the commercial Pt catalyst. Also, it maintains steady hydrogen bubble evolution even after 30 000 potential cycles in acid media. Furthermore, the RuRh2 bimetallene nanoring shows an outstanding activity in both alkaline and neutral media, outperforming that of Pt catalysts and other reported HER catalysts. A combination of atomic-scale structure observation and density functional theory calculations demonstrates that both the grain boundaries and symmetry breaking of RuRh2 bimetallene cannot only weaken the adsorption strength of atomic hydrogen, but also facilitate the transfer of electrons and the adsorption of reactants, further boosting the HER electrocatalytic performance in all pH values.
ABSTRACT
Defect engineering is widely applied in transition metal dichalcogenides to produce high-purity hydrogen. However, the instability of vacancy states on catalysis still remains a considerable challenge. Here, our first-principles calculations showed that, by optimizing the asymmetric S vacancy in the highly asymmetric 1T' crystal of layered bitransition metal dichalcogenides (Co-MoS2) in light of Pd modulation, the relative amount of metastable phase and the quantity of active sites in the structure can be reduced and increased, respectively, leading to a further boosted hydrogen evolution reaction (HER) activity toward layered bi-transition metal dichalcogenides. Thus, we then used a "click" chemistry strategy to make such a catalyst with engineered unsaturated sulfur edges via a strong coupling effect between ultrafine Pd ensembles and Co-MoS2 nanosheets. As expected, the Pd-modulated Co-MoS2 nanosheets exhibited a very low overpotential of 60 mV at 10 mA cm-2 with a small Tafel slope (56 mV dec-1) for the HER in 1.0 M PBS, comparable to those of commercial Pt/C. In addition, their high HER activity was retained in acidic and alkaline conditions. Both the theoretical and experimental results revealed that Pd ensembles can efficiently activate and stabilize the inert basal plane S sites during HER processes as a result of the formation of Pd-S in Co-MoS2. This work not only provides a deeper understanding of the correlation between defect sites and intrinsic HER catalytic properties for transition metal chalcogenide (TMD)-based catalysts, but also offers new insights into better designing earth-abundant HER catalysts displaying high efficiency and durability.
ABSTRACT
Low-cost and highly effective catalysts are crucial to the electrocatalytic hydrogen evolution reaction (HER). Among non-noble catalysts, molybdenum carbides are promising candidates because of their high reserves, stability, low cost, and structural diversity. In this work, we report a simple method to fabricate a hollow porous Mo2C@C nanoball through a hydrothermal preparation process of molybdenum precursors at high temperatures. Specifically, we have combined interfacial polymerization and the chelation effect to synthesize the Mo-polydopamine (Mo-PDA) precursor. As a result, Mo2C@C-3 only requires an ultralow Tafel slope (~55 mV dec-1) and low overpotential (η50 ≈ 167 mV) in a 0.5 M H2SO4 solution with long-term cycling stability. Besides, it also exhibits outstanding activity and stability under extensive HER testing in alkaline media. This study is promising for the development of advanced molybdenum carbide electrocatalysts toward electrochemical applications.
ABSTRACT
Introduction of surface defects and phase control engineering in the electrocatalytic system of overall water splitting has played a crucial role in significantly enhancing its electrocatalytic activity toward the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in water splitting, but the relationship between structure and electrocatalysis is still elusive. Herein, we report a solid-liquid method to induce surface reorganization (formation of a chalcogenide layer with rich chalcogenide vacancies) and phase transformation (Co9S8-to-Co3S4) simultaneously on cobalt chalcogenide. Featuring a uniform 2D morphology and the in situ formation of sulfur (S) vacancies, in a 0.1 M KOH solution, it exhibits a low overpotential of 288 mV vs. RHE at 10 mA cm-2, a low Tafel slope of 43.4 mV dec-1, and strong cycling stability (35 h), outperforming commercial RuO2 and most reported OER electrocatalysts. In addition, we also investigate the OER activity of the Co-S-P electrode in 1.0 M KOH solutions. Co0.37S0.38P0.02 NSs only need 257 mV to reach a current density of 10 mA cm-2. Meanwhile, the Tafel slope of Co0.37S0.38P0.02 NSs (44.0 mV dec-1) is lower than those of other recently reported electrocatalysts. Also, it shows high HER electrocatalytic activity in alkaline and acidic solutions. Finally, the Co0.37S0.38P0.02 electrode is used as a cathode and anode simultaneously for overall water splitting, which merely requires a cell voltage of 1.59 V at 10 mA cm-2 with excellent stability (40 h).
