RESUMEN
Improving kinetics of solid-state sulfide conversion in sulfur cathodes can enhance sulfur utilization of metal-sulfur batteries. However, fundamental understanding of the solid-state conversion remains to be achieved. Here, taking potassium-sulfur batteries as a model system, we for the first time report the reducing overpotential of solid-state sulfide conversion via the meta-stable S3 2- intermediates on transition metal single-atom sulfur hosts. The catalytic sulfur host containing Cu single atoms demonstrates high capacities of 1595 and 1226â mAh g-1 at current densities of 335 and 1675â mA g-1 , respectively, with stable Coulombic efficiency of ≈100 %. Combined spectroscopic characterizations and theoretical computations reveal that the relatively weak Cu-S bonding results in low overpotential of solid-state sulfide conversion and high sulfur utilization. The elucidation of solid-state sulfide conversion mechanism can direct the exploration of highly efficient metal-sulfur batteries.
RESUMEN
Decarbonizing N2 conversion is particularly challenging, but essential for sustainable development of industry and agriculture. Herein, we achieve electrocatalytic activation/reduction of N2 on X/Fe-N-C (X=Pd, Ir and Pt) dual-atom catalysts under ambient condition. We provide solid experimental evidence that local hydrogen radical (H*) generated on the X site of the X/Fe-N-C catalysts can participate in the activation/reduction of N2 adsorbed on the Fe site. More importantly, we reveal that the reactivity of X/Fe-N-C catalysts for N2 activation/reduction can be well adjusted by the activity of H* generated on the X site, i.e., the interaction between the X-H bond. Specifically, X/Fe-N-C catalyst with the weakest X-H bonding exhibits the highest H* activity, which is beneficial to the subsequent cleavage of X-H bond for N2 hydrogenation. With the most active H*, the Pd/Fe dual-atom site promotes the turnover frequency of N2 reduction by up to 10 times compared with the pristine Fe site.
RESUMEN
Copper is the only metal catalyst that can perform the electrocatalytic CO2 reduction reaction (CRR) to produce hydrocarbons and oxygenates. Its surface oxidation state determines the reaction pathway to various products. However, under the cathodic potential of CRR conditions, the chemical composition of most Cu-based catalysts inevitably undergoes electroreduction from Cu2+ to Cu0 or Cu1+ species, which is generally coupled with phase reconstruction and the formation of new active sites. Since the initial Cu2+ active sites are hard to retain, there have been few studies about Cu2+ catalysts for CRR. Herein we propose a solid-solution strategy to stabilize Cu2+ ions by incorporating them into a CeO2 matrix, which works as a self-sacrificing ingredient to protect Cu2+ active species. In situ spectroscopic characterization and density functional theory calculations reveal that compared with the conventionally derived Cu catalysts with Cu0 or Cu1+ active sites, the Cu2+ species in the solid solution (Cu-Ce-Ox) can significantly strengthen adsorption of the *CO intermediate, facilitating its further hydrogenation to produce CH4 instead of dimerization to give C2 products. As a result, different from most of the other Cu-based catalysts, Cu-Ce-Ox delivered a high Faradaic efficiency of 67.8% for CH4 and a low value of 3.6% for C2H4.
RESUMEN
Noble metals have broad prospects for catalytic applications yet are restricted to a few packing modes with limited structural flexibility. Here, we achieved geometric structure diversification of noble metals by integrating spatially correlated noble metal single atoms (e.g., Pt, Pd, and Ru) into the lattice of transition metal oxides (TMOs, e.g., Co3O4, Mn5O8, NiO, Fe2O3). The obtained noble metal single atoms exhibited distinct topologies (e.g., crs, fcu-hex-pcu, fcu, and bcu-x) from those of conventional metallic phases. For example, Pt single atoms with a crs topology (Ptcrs-Co3O4) are endowed with synergy of metal-metal and metal-support interactions. A quantitative relationship between various Pt topologies determined by TMO substrates and their electrocatalytic activities was established. We anticipate that this type of interactive single-atom catalysts can bridge the geometric, topological, and electronic structure gaps between the "close-packed" nanoparticles and isolated single atoms as two common categories of heterogeneous catalysts.
RESUMEN
Single-atom catalysts (SACs) hold great promise for highly efficient heterogeneous catalysis, yet the practical applications require the development of high-density active sites with flexible geometric structures. The lack of understanding in the dynamic formation process of single atoms in the host framework has been plaguing the controllable synthesis of next generation SACs. Here using Co-based metal-organic frameworks (MOFs) as a starting substrate, we fully elucidated the formation of high-density Pt single atoms with inter-site interactions in derived Co3 O4 host. The cation exchange process and dynamic evolution of Pt-Pt interactions, organic ligand cleavage and Pt-oxygen coordination formation during the pyrolysis process have been unambiguously interpreted by a series of in situ/ex situ spectroscopic measurements and theoretical computation. These findings would direct the synthesis of high-density SACs with metal-metal interactions, which demonstrate significantly enhanced structural flexibility and catalytic properties.
RESUMEN
Potassium-sulfur batteries hold practical promise for next-generation batteries because of their high theoretical gravimetric energy density and low cost. However, significant impediments are the sluggish K2S oxidation kinetics and a lack of atomic-level understanding of K2S oxidation. Here, for the first time, we report the catalytic oxidation of K2S on a sulfur host with Co single atoms immobilized on nitrogen-doped carbon. On the basis of combined spectroscopic characterizations, electrochemical evaluation, and theoretical computations, we show a synergistic effect of dynamic Co-S and N-K interactions to catalyze K2S oxidation. The resultant potassium-sulfur battery exhibited high capacities of 773 and 535 mAh g-1 under high current densities of 1 and 2 C, respectively. These findings provide atomic-scale insights for the rational design of highly efficient sulfur hosts.
RESUMEN
Noble metals manifest themselves with unique electronic structures and irreplaceable activity toward a wide range of catalytic applications but are unfortunately restricted by limited choice of geometric structures spanning single atoms, clusters, nanoparticles, and bulk crystals. Herein, we propose how to overcome this limitation by integrating noble metal atoms into the lattice of transition metal oxides to create a new type of hybrid structure. This study shows that iridium single atoms can be accommodated into the cationic sites of cobalt spinel oxide with short-range order and an identical spatial correlation as the host lattice. The resultant Ir0.06Co2.94O4 catalyst exhibits much higher electrocatalytic activity than the parent oxide by 2 orders of magnitude toward the challenging oxygen evolution reaction under acidic conditions. Because of the strong interaction between iridium and cobalt oxide support, the Ir0.06Co2.94O4 catalyst shows significantly improved corrosion resistance under acidic conditions and oxidative potentials. This work eliminates the "close-packing" limitation of noble metals and offers promising opportunity to create analogues with desired topologies for various catalytic applications.
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Owing to dwindling fossil fuels reserves, the development of alternative renewable energy sources is globally important. Photocatalytic hydrogen (H2 ) evolution represents a practical and affordable alternative to convert sunlight into carbon-free H2 fuel. Recently, 2D/2D van der Waals heterostructures (vdWHs) have attracted significant research attention for photocatalysis. Here, for the first time a ReS2 /In2 ZnS4 2D/2D vdWH synthesized via a facile physical mixing is reported. It exhibits a highly promoted photocatalytic H2 -evolution rate of 2515 µmol h-1 g-1 . Importantly, this exceeds that for pristine In2 ZnS4 by about 22.66 times. This, therefore, makes ReS2 /In2 ZnS4 one of the most efficient In2 ZnS4 -based photocatalysts without noble-metal cocatalysts. Advanced characterizations and theoretical computations results show that interlayer electronic interaction within ReS2 /In2 ZnS4 vdWH and atomic-level S active centers along the edges of ReS2 NSs work collaboratively to result in the boosted light-induced H2 evolution. Results will be of immediate benefit in the rational design and preparation of vdWHs for applications in catalysis/(opto)electronics.
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The development of all-solid-state lithium-sulfur batteries (ASSLSBs) toward large-scale electrochemical energy storage is driven by the higher specific energies and lower cost in comparison with the state-of-the-art Li-ion batteries. Yet, insufficient mechanistic understanding and quantitative parameters of the key components in sulfur-based cathode hinders the advancement of the ASSLSB technologies. This review offers a comprehensive analysis of electrode parameters, including specific capacity, voltage, S mass loading and S content toward establishing the specific energy (Wh kg-1) and energy density (Wh L-1) of the ASSLSBs. Additionally, this work critically evaluates the progress in enhancing lithium ion and electron percolation and mitigating electrochemical-mechanical degradation in sulfur-based cathodes. Last, a critical outlook on potential future research directions is provided to guide the rational design of high-performance sulfur-based cathodes toward practical ASSLSBs.
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The exploration of post-Lithium (Li) metals, such as Sodium (Na), Potassium (K), Magnesium (Mg), Calcium (Ca), Aluminum (Al), and Zinc (Zn), for electrochemical energy storage has been driven by the limited availability of Li and the higher theoretical specific energies compared to the state-of-the-art Li-ion batteries. Post-Li metal||S batteries have emerged as a promising system for practical applications. Yet, the insufficient understanding of quantitative cell parameters and the mechanisms of sulfur electrocatalytic conversion hinder the advancement of these battery technologies. This perspective offers a comprehensive analysis of electrode parameters, including S mass loading, S content, electrolyte/S ratio, and negative/positive electrode capacity ratio, in establishing the specific energy (Wh kg-1) of post-Li metal||S batteries. Additionally, we critically evaluate the progress in investigating electrochemical sulfur conversion via homogeneous and heterogeneous electrocatalytic approaches in both non-aqueous Na/K/Mg/Ca/Al||S and aqueous Zn||S batteries. Lastly, we provide a critical outlook on potential research directions for designing practical post-Li metal||S batteries.
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Aqueous Zn-ion batteries hold practical promise for large-scale energy storage because of the safety and affordability of aqueous-based electrolytes; in addition, the manufacturing process is significantly simplified by direct employment of Zn metal as an anode. However, hydrogen evolution due to near-surface water dissociation has hindered large-scale applications of them. Here, we report the suppression of the hydrogen evolution reaction via a CuN3-coordinated graphitic carbonitride (CuN3-C3N4) anticatalytic interface to achieve highly efficient aqueous Zn-ion batteries. Based on in situ gas chromatography and in situ synchrotron-based X-ray diffraction spectroscopy, we demonstrated that the hydrogen evolution reaction triggers the Zn4SO4(OH)6·xH2O formation. A combination of in situ infrared spectroscopy and density functional theory simulations has proved to stabilize near-surface H3O+ species and regulate adsorption of H* intermediates by an anticatalytic interface for hydrogen evolution reaction suppression. Consequently, the anticatalytic interface greatly improves the Coulombic efficiency of Zn plating/stripping to â¼99.7% for 5500 cycles and the cycling reversibility to over 1300 h at 1 mA cm-2 and 1 mAh cm-2. With an anticatalytic interface, the full cell shows an excellent Coulombic efficiency of 98.3% over 400 cycles at 1C. These findings provide strategic insight for targeted designing of highly efficient aqueous Zn-ion batteries.
RESUMEN
Single-atom catalysts (SACs) offer significant potential across various applications, yet our understanding of their formation mechanism remains limited. Notably, the pyrolysis of zeolitic imidazolate frameworks (ZIFs) stands as a pivotal avenue for SAC synthesis, of which the mechanism can be assessed through infrared (IR) spectroscopy. However, the prevailing analysis techniques still rely on manual interpretation. Here, we report a machine learning (ML)-driven analysis of the IR spectroscopy to unravel the pyrolysis process of Pt-doped ZIF-67 to synthesize Pt-Co3O4 SAC. Demonstrating a total Pearson correlation exceeding 0.7 with experimental data, the algorithm provides correlation coefficients for the selected structures, thereby confirming crucial structural changes with time and temperature, including the decomposition of ZIF and formation of Pt-O bonds. These findings reveal and confirm the formation mechanism of SACs. As demonstrated, the integration of ML algorithms, theoretical simulations, and experimental spectral analysis introduces an approach to deciphering experimental characterization data, implying its potential for broader adoption.
RESUMEN
Single-atom catalysts (SACs) include a promising family of electrocatalysts with unique geometric structures. Beyond conventional ones with fully isolated metal sites, an emerging class of catalysts with the adjacent metal single atoms exhibiting intersite metal-metal interactions appear in recent years and can be denoted as correlated SACs (C-SACs). This type of catalysts provides more opportunities to achieve substantial structural modification and performance enhancement toward a wider range of electrocatalytic applications. On the basis of a clear identification of metal-metal interactions, this review critically examines the recent research progress in C-SACs. It shows that the control of metal-metal interactions enables regulation of atomic structure, local coordination, and electronic properties of metal single atoms, which facilitate the modulation of electrocatalytic behavior of C-SACs. Last, we outline directions for future work in the design and development of C-SACs, which is indispensable for creating high-performing new SAC architectures.
RESUMEN
Designing catalytic materials with enhanced stability and activity is crucial for sustainable electrochemical energy technologies. RuO2 is the most active material for oxygen evolution reaction (OER) in electrolysers aiming at producing 'green' hydrogen, however it encounters critical electrochemical oxidation and dissolution issues during reaction. It remains a grand challenge to achieve stable and active RuO2 electrocatalyst as the current strategies usually enhance one of the two properties at the expense of the other. Here, we report breaking the stability and activity limits of RuO2 in neutral and alkaline environments by constructing a RuO2/CoOx interface. We demonstrate that RuO2 can be greatly stabilized on the CoOx substrate to exceed the Pourbaix stability limit of bulk RuO2. This is realized by the preferential oxidation of CoOx during OER and the electron gain of RuO2 through the interface. Besides, a highly active Ru/Co dual-atom site can be generated around the RuO2/CoOx interface to synergistically adsorb the oxygen intermediates, leading to a favourable reaction path. The as-designed RuO2/CoOx catalyst provides an avenue to achieve stable and active materials for sustainable electrochemical energy technologies.
RESUMEN
High-performance and low-cost photocatalysts play the key role in achieving the large-scale solar hydrogen production. In this work, we report a liquid-exfoliation approach to prepare NiPS3 ultrathin nanosheets as a versatile platform to greatly improve the light-induced hydrogen production on various photocatalysts, including TiO2, CdS, In2ZnS4 and C3N4. The superb visible-light-induced hydrogen production rate (13,600 µmol h-1 g-1) is achieved on NiPS3/CdS hetero-junction with the highest improvement factor (~1,667%) compared with that of pure CdS. This significantly better performance is attributed to the strongly correlated NiPS3/CdS interface assuring efficient electron-hole dissociation/transport, as well as abundant atomic-level edge P/S sites and activated basal S sites on NiPS3 ultrathin nanosheets advancing hydrogen evolution. These findings are revealed by the state-of-art characterizations and theoretical computations. Our work for the first time demonstrates the great potential of metal phosphorous chalcogenide as a general platform to tremendously raise the performance of different photocatalysts.
RESUMEN
As the most promising alternative to platinum-based catalysts for cathodic oxygen reduction reaction (ORR) in proton exchange membrane fuel cells, further performance enhancement of Fe-N-C catalysts is highly expected to promote their wide application. In Fe-N-C catalysts, the single Fe atom forms a square-planar configuration with four adjacent N atoms (D4h symmetry). Breaking the D4h symmetry of the FeN4 active center provides a new route to boost the activity of Fe-N-C catalysts. Herein, for the first time, the deformation of the square-planar coordination of FeN4 moiety achieved by introducing chalcogen oxygen groups (XO2 , X = S, Se, Te) as polar functional groups in the Fe-N-C catalyst is reported. The theoretical and experimental results demonstrate that breaking the D4h symmetry of FeN4 results in the rearrangement of Fe 3d electrons and increases spin moment of Fe centers. The efficient spin state manipulation optimizes the adsorption energetics of ORR intermediates, thereby significantly promoting the intrinsic ORR activity of Fe-N-C catalysts, among which the SeO2 modified catalyst lies around the peak of the ORR volcano plot. This work provides a new strategy to tune the local coordination and thus the electronic structure of single-atom catalysts.
RESUMEN
Metal sulfides electrodeposition in sulfur cathodes mitigates the shuttle effect of polysulfides to achieve high Coulombic efficiency in secondary metal-sulfur batteries. However, fundamental understanding of metal sulfides electrodeposition and kinetics mechanism remains limited. Here using room-temperature sodium-sulfur cells as a model system, we report a Mo5N6 cathode material that enables efficient Na2S electrodeposition to achieve an initial discharge capacity of 512 mAh g-1 at a specific current of 1â675 mA g-1, and a final discharge capacity of 186 mAh g-1 after 10,000 cycles. Combined analyses from synchrotron-based spectroscopic characterizations, electrochemical kinetics measurements and density functional theory computations confirm that the high d-band position results in a low Na2S2 dissociation free energy for Mo5N6. This promotes Na2S electrodeposition, and thereby favours long-term cell cycling performance.
RESUMEN
Confinement of polysulfides in sulfur cathodes is pivotal for eliminating the "shuttle effect" in metal-sulfur batteries, which represent promising solutions for large-scale and sustainable energy storage. However, mechanistic exploration and in-depth understanding for the confinement of polysulfides remain limited. Consequently, it is a critical challenge to achieve highly stable metal-sulfur batteries. Here, based on a 2D metal-organic framework (2D MOF), a new mechanism to realize effective confinement of polysulfides is proposed. A combination of in situ synchrotron X-ray diffraction, electrochemical measurements, and theoretical computations reveal that the dynamic electron states of the Ni centers in the 2D MOF enable the interaction between polysulfides and the MOF in the discharge/charge process to be tuned, resulting in both strong adsorption and fast conversion kinetics of polysulfides. The resultant room-temperature sodium-sulfur batteries are amongst the most stable reported so far, thus demonstrating that the new mechanism opens a promising avenue for the development of high-performance metal-sulfur batteries.
RESUMEN
The establishment of electrocatalysts with bifunctionality for efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acidic environments is necessary for the development of proton exchange membrane (PEM) water electrolyzers for the production of clean hydrogen fuel. RuIr alloy is considered to be a promising electrocatalyst because of its favorable OER performance and potential for HER. Here, the design of a bifunctional electrocatalyst with greatly boosted water-splitting performance from doping RuIr alloy nanocrystals with transition metals that modify electronic structure and binding strength of reaction intermediates is reported. Significantly, Co-RuIr results in small overpotentials of 235 mV for OER and 14 mV for HER (@ 10 mA cm-2 current density) in 0.1 m HClO4 media. Therefore a cell voltage of just 1.52 V is needed for overall water splitting to produce hydrogen and oxygen. More importantly, for a series of M-RuIr (M = Co, Ni, Fe), the catalytic activity dependence at fundamental level on the chemical/valence states is used to establish a novel composition-activity relationship. This permits new design principles for bifunctional electrocatalysts.