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1.
Nat Mater ; 2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38671162

RESUMO

Oxided-dispersion-strengthened (ODS) alloys are promising high-strength materials used in extreme environments such as high-temperature and radiation tolerance applications. Until now, ODS alloys have been developed for reducible metals by chemical processing methods, but there are no commercially available ODS alloys for unreducible metals, namely, Al, Mg, Ti, Zr and so on, owing to the challenge of uniformly dispersing oxide particles in these alloys by traditional techniques. Here we present a strategy to achieve ODS Al alloys containing highly dispersive 5 nm MgO nanoparticles by powder metallurgy, using nanoparticles that have in situ-grown graphene-like coatings and hence largely reduced surface energy. Notably, the densely dispersed MgO nanoparticles, which have a fully coherent relationship with an Al matrix, show effective suppression of interfacial vacancy diffusion, thus leading to unprecedented strength (~200 MPa) and creep resistance at temperatures as high as 500 °C. Our processing approach should enable the dispersion of ultrafine nanoparticles in a wide range of alloys for high-temperature-related applications.

2.
Angew Chem Int Ed Engl ; : e202401238, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38651232

RESUMO

Emerging high entropy compounds (HECs) have attracted huge attention in electrochemical energy-related applications. The features of ultrafine size and carbon incorporation show great potential to boost the ion-storage kinetics of HECs. However, they are rarely reported because high-temperature calcination tends to result in larger crystallites, phase separation, and carbon reduction. Herein, using the NaCl self-assembly template method, by introducing a high-pressure field in the calcination process, the atom diffusion and phase separation are inhibited for the general formation of HECs, and the HEC aggregation is inhibited for obtaining ultrafine size. The general preparation of ultrafine-sized (<10 nm) HECs (nitrides, oxides, sulfides, and phosphates) anchored on porous carbon composites is realized. They are demonstrated by combining advanced characterization technologies with theoretical computations. Ultrafine-sized high entropy sulfides-MnFeCoCuSnMo/porous carbon (HES-MnFeCoCuSnMo/PC) as representative anodes exhibit excellent sodium-ion storage kinetics and capacities (a high rating capacity of 278 mAh g-1 at 10 A g-1 for full cell and a high cycling capacity of 281 mAh g-1 at 20 A g-1 after 6000 cycles for half cell) due to the combining advantages of high entropy effect, ultrafine size, and PC incorporation. Our work provides a new opportunity for designing and fabricating ultrafine-sized HECs.

3.
ACS Appl Mater Interfaces ; 16(13): 16351-16362, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38515323

RESUMO

Poly(ethylene oxide) (PEO)-based electrolytes have been extensively studied for all-solid-state lithium-metal batteries due to their excellent film-forming capabilities and low cost. However, the limited ionic conductivity and poor mechanical strength of the PEO-based electrolytes cannot prevent the growth of undesirable lithium dendrites, leading to the failure of batteries. Metal-organic frameworks (MOFs) are functional materials with a periodic porous structure that can improve the electrochemical performance of PEO-based electrolytes. However, the enhancement effect of MOFs with different metal centers and the interaction mechanism with PEO remain unclear. Herein, MOF-74s with Cu or Ni centers are prepared and used as fillers of PEO-based electrolytes. Adding 15 wt % of Cu-MOF-74 to the PEO-based electrolyte (15%Cu-MOF/P-Li) effectively improves the ionic conductivity, lithium transference number, and mechanical strength of the PEO-based electrolyte simultaneously. Furthermore, the ordered pore channels of Cu-MOF-74 provide uniform Li-ion transport pathways, facilitating homogeneous Li+ deposition. As a result, the lithium symmetric cell with 15%Cu-MOF/P-Li shows stable cycles for 1080 h at 0.1 mA cm-2 and 0.1 mAh cm-2, and the Li | 15% Cu-MOF/P-Li | LFP full cell exhibits a long cycle life up to 200 cycles at 60 °C and 0.5 C, with a capacity retention rate of 89.7%.

4.
Cancer Cell Int ; 24(1): 117, 2024 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-38549127

RESUMO

BACKGROUND: Multiple myeloma (MM) is the second most common refractory hematologic cancer. Searching for new targets and prognostic markers for MM is significant. METHODS: GSE39754, GSE6477 and GSE24080 were downloaded from the Gene Expression Omnibus (GEO) database. Differentially expressed genes (DEGs) in MM versus healthy people from GSE39754 and GSE6477 were screened using limma package, and MM-related module genes were chosen with the use of Weighted gene co-expression network analysis (WGCNA), and the two were intersected using ggVennDiagram for obtaining MM-related DEGs. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) analyses were carried out. Then, protein-protein interactions (PPI) analysis in String database was used to obtain hub genes, while prognosis was analyzed by survival package in GSE24080. Receiver operating characteristic (ROC) curve was adopted for evaluating diagnostic value of hub genes. Besides, univariable/multivariable Cox regression were employed to screen independent prognostic biomarkers. Gene set enrichment analysis (GSEA) was used to find possible mechanism. Finally, western-blotting and reverse transcription-polymerase chain reaction (RT-PCR) verify TYROBP expression within MM and healthy people. We performed cell adhesion and transwell assays for investigating TYROBP function in MM cell adhesion and migration. RESULTS: Through differential analyses, 92 MM-related DEGs were obtained. 10 hub genes were identified by PPI and CytoHubba. Their diagnostic and prognostic significance was analyzed. Down-regulation of genes like TYROBP, ELANE, MNDA, and MPO related to dismal MM prognosis. Upon univariable/multivariable Cox regression, TYROBP independently predicted MM prognosis. GSEA pathway was enriched, indicating that TYROBP expression affected MM development via cell adhesion molecular pathway. Upon Western-blotting and RT-PCR assays, TYROBP expression among MM patients decreased relative to healthy donors. Cell adhesion and transwell migration assays revealed increased MM cell adhesion and decreased migration upon TYROBP up-regulation. CONCLUSION: In summary, TYROBP is a potential prognostic marker for MM.

5.
Angew Chem Int Ed Engl ; 63(13): e202317256, 2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38289336

RESUMO

Powdery hexagonal boron nitride (h-BN), as an important material for electrochemical energy storage, has been typically synthesized in bulk and one/two-dimensional (1/2D) nanostructured morphologies. However, until now, no method has been developed to synthesize powdery three-dimensional (3D) h-BN. This work introduces a novel NaCl-glucose-assisted strategy to synthesize micron-sized 3D h-BN with a honeycomb-like structure and its proposed formation mechanism. We propose that NaCl acts as the template of 3D structure and promotes the nitridation reaction by adsorbing NH3 . Glucose facilitates the homogeneous coating of boric acid onto the NaCl surface via functionalizing the NaCl surface. During the nitridation reaction, boron oxides (BO4 and BO3 ) form from a dehydration reaction of boric acid, which is then reduced to O2 -B-N and O-B-N2 intermediates before finally being reduced to BN3 by NH3 . When incorporated into polyethylene oxide-based electrolytes for Li metal batteries, 5 wt % of 3D h-BN significantly enhances ionic conductivity and mechanical strength. Consequently, this composite electrolyte demonstrates superior electrochemical stability. It delivers 300 h of stable cycles in the Li//Li cell at 0.1 mA cm-2 and retains 89 % of discharge capacity (138.9 mAh g-1 ) after 100 cycles at 1 C in the LFP//Li full cell.

6.
Angew Chem Int Ed Engl ; 63(1): e202316116, 2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-37983741

RESUMO

The water-soluble salt-template technique holds great promise for fabricating 3D porous materials. However, an equipment-free and pore-size controllable synthetic approach employing salt-template precursors at room temperature has remained unexplored. Herein, we introduce a green room-temperature antisolvent precipitation strategy for creating salt-template self-assembly precursors to universally produce 3D porous materials with controllable pore size. Through a combination of theoretical simulations and advanced characterization techniques, we unveil the antisolvent precipitation mechanism and provide guidelines for selecting raw materials and controlling the size of precipitated salt. Following the calcination and washing steps, we achieve large-scale and universal production of 3D porous materials and the recycling of the salt templates and antisolvents. The optimized nitrogen-doped 3D porous carbon (N-3DPC) materials demonstrate distinctive structural benefits, facilitating a high capacity for potassium-ion storage along with exceptional reversibility. This is further supported by in situ electrochemical impedance spectra, in situ Raman spectroscopy, and theoretical calculations. The anode shows a high rate capacity of 181 mAh g-1 at 4 A g-1 in the full cell. This study addresses the knowledge gap concerning the room-temperature synthesis of salt-template self-assembly precursors for the large-scale production of porous materials, thereby expanding their potential applications for electrochemical energy conversion and storage.

7.
Phys Chem Chem Phys ; 25(48): 32989-32999, 2023 Dec 13.
Artigo em Inglês | MEDLINE | ID: mdl-38032048

RESUMO

Changing the composition is an important way to regulate the electrocatalytic performance of the oxygen evolution reaction (OER) for metallic compounds. Clarifying the synergistic mechanism among different compositions is a key scientific problem to be solved urgently. Here, based on first-principles calculations, a Ni-O-Fe multisite dynamic synergistic reaction mechanism (MDSM) for the OER of Fe-doped NiOOH (NiFeOOH) has been discovered. Based on the MDSM, Fe/O/Ni are triggered as the active sites in turn, resulting in an overpotential of 0.33 V. The factors affecting the deprotonation, O-O coupling, and O2 desorption during the OER process are analyzed. The electron channels related to the magnetic states among Fe-O-Ni is revealed, which results in the decoupling between OER sites and the oxidation reaction sites. O-O coupling and O2 desorption are affected by ferromagnetic coupling and the instability of the lattice O during the OER process, respectively. The results give a comprehensive understanding of the active sites in NiFeOOH and provide a new perspective on the synergistic effects among different compositions in metal compounds during the OER process.

8.
Chem Soc Rev ; 52(22): 7802-7847, 2023 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-37869994

RESUMO

To support the global goal of carbon neutrality, numerous efforts have been devoted to the advancement of electrochemical energy conversion (EEC) and electrochemical energy storage (EES) technologies. For these technologies, transition metal dichalcogenide/carbon (TMDC/C) heterostructures have emerged as promising candidates for both electrode materials and electrocatalysts over the past decade, due to their complementary advantages. It is worth noting that interfacial properties play a crucial role in establishing the overall electrochemical characteristics of TMDC/C heterostructures. However, despite the significant scientific contribution in this area, a systematic understanding of TMDC/C heterostructures' interfacial engineering is currently lacking. This literature review aims to focus on three types of interfacial engineering, namely interfacial orientation engineering, interfacial stacking engineering, and interfacial doping engineering, of TMDC/C heterostructures for their potential applications in EES and EEC devices. To accomplish this goal, a combination of experimental and theoretical approaches was used to allow the analysis and summary of the fundamental electrochemical properties and preparation strategies of TMDC/C heterostructures. Moreover, this review highlights the design and utilization of the interfacial engineering of TMDC/C heterostructures for specific EES and EEC devices. Finally, the challenges and opportunities of using interfacial engineering of TMDC/C heterostructures in practical EES and EEC devices are outlined. We expect that this review will effectively guide readers in their understanding, design, and application of interfacial engineering of TMDC/C heterostructures.

9.
Adv Mater ; 35(52): e2307209, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37729880

RESUMO

The sub-10 nm metal-based nanomaterials (SMNs) show great potential for the electrochemical energy storage field. However, their ion storage capacity and stability suffer from severe agglomeration and interface problems. Herein, a universal strategy is reported to synthesize a wide range of SMNs (e.g., metal, nitride, oxide, and sulfides) embedded in free-standing carbon foam (SMN/FC-F) composite electrodes by crossing the interfacial confinement of NaCl self-assembly with the thermal-mechanical coupling of powder metallurgy. The pressure-enhanced NaCl self-assembly interfacial confinement is greatly beneficial to preventing SMN agglomeration and promoting SMNs embedded in FC-F which originate from the welding of carbon nanosheets. They are confirmed via a series of advanced characterizations including X-ray photoelectron spectroscopy, and spherical aberration-corrected scanning transmission electron microscopy, with theoretical computations. Benefiting from the unique structure, SMNs/FC-F delivers ultrafast and stable ion-storage kinetics. As a proof-of-concept demonstration, the MoS2 /FC-F shows excellent ion storage kinetics and superior long-term cycling performance for ion storage (e.g., Na3 V2 (PO4 )2 O2 F/C//MoS2 /FC-F sodium-ion batteries exhibit a high reversible capacity of 185 mAh g-1 at 0.5 A g-1 with a decay rate of 0.05% per cycle.). This work provides a new opportunity to design and fabricate promising SMN-based free-standing working electrodes for electrochemical energy storage and conversion applications.

10.
ACS Appl Mater Interfaces ; 15(32): 38423-38432, 2023 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-37527430

RESUMO

The main obstacle to the development of large-scale electrochemical hydrogen production based on water splitting is the slow four-electron kinetics of OER (oxygen evolution reaction). The most efficient method is to create sophisticated and effective OER catalysts. Here, we proposed the controlled synthesis of high-entropy layered double hydroxides (HELDH) for wide component regulation and the component design of high OER activity to make up for the restricted component regulation in conventional catalysts. Through the use of coprecipitation and hydrothermal synthesis, the representative sample (MgCoNi)3(FeAl)-LDH is created and systematically characterized. Significantly, this technique of preparation may generically synthesize a variety of HELDH with various component combinations, demonstrating the remarkable adaptability of the HELDH components. Subsequently, (FeCoNi)3(FeCr)-LDH with high OER activity is designed and synthesized. (FeCoNi)3(FeCr)-LDH shows excellent OER activity (overpotential is only 230 mV at 10 mA cm-2). A new platform for the creation of high-performance catalysts and high-entropy materials was established by the synthesis and design of HELDH.

11.
Angew Chem Int Ed Engl ; 62(22): e202302640, 2023 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-36964969

RESUMO

The advent of wearable electronics has strongly stimulated advanced research into the exploration of flexible zinc-air batteries (ZABs) with high theoretical energy density, high inherent safety, and low cost. However, the half-open battery structure and the high concentration of alkaline aqueous environment pose great challenges on the electrolyte retention capability and the zinc anode stability. Herein, a starch-based superabsorbent hydrogel polymer electrolyte (SSHPE) with high ionic conductivity, electrolyte absorption and retention capabilities, strong alkaline resistance and high zinc anode stability has been designed and applied in ZABs. Experimental and calculational analyses probe into the root of the superiority of SSHPEs, confirming the significance of the carboxyl functional groups along their polymer chains. These features endow the as-fabricated ZAB a long cycle life of 300 h, much longer than that with commonly used poly(vinyl alcohol)-based electrolyte.

12.
Small ; 19(27): e2208095, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36965039

RESUMO

Constructing a 3D composite Li metal anode (LMA) along with the engineering of artificial solid electrolyte interphase (SEI) is a promising strategy for achieving dendrite-free Li deposition and high cycling stability. The nanostructure of artificial SEI is closely related to the performance of the LMA. Herein, the self-grown process and morphology of in situ formed Li2 S during lithiation of Cux S is studied systematically, and a large-sized sheet-like Li2 S layer as an artificial SEI is in situ generated on the inner surface of a 3D continuous porous Cu skeleton (3DCu@Li2 S-S). The sheet-like Li2 S layer with few interfacial pitfalls (Cu/Li2 S heterogeneous interface) possesses enhanced diffusion of Li ions. And the continuous porous structure provides transport channels for lithium-ion transport. As a result, the 3DCu@Li2 S-S presents a high Coulombic efficiency (99.3%), long cycle life (500 cycles), and high-rate performance (10 mA cm-2 ). Furthermore, Li/3DCu@Li2 S anode fabricated by thermal infusion method inherits the synergistic advantages of sheet-like Li2 S and continuous porous structure. The Li/3DCu@Li2 S anode shows significantly enhanced cycling life in both liquid and solid electrolytes. This work provides a new concept to design artificial SEI for LMA with high safe and high performance.

13.
Zhongguo Shi Yan Xue Ye Xue Za Zhi ; 31(1): 8-16, 2023 Feb.
Artigo em Chinês | MEDLINE | ID: mdl-36765470

RESUMO

OBJECTIVE: To explore the expression pattern and clinical significance of Integral membrane protein 2A(ITM2A) in drug resistant patients with chronic myeloid leukemia (CML). METHODS: The expression of ITM2A in CML was evaluated by qRT-PCR, Western blot and immunocytochemistry. In order to understand the possible biological effects of ITM2A, apoptosis, cell cycle and myeloid differentiation antigen expression of CML cells were detected by flow cytometry after over-expression of ITM2A. The nuderlying molecular mechanism of its biological effect was explored. RESULTS: The expression of ITM2A in bone marrow of CML resistant patients was significantly lower than that of sensitive patients and healthy donors(P<0.05). The CML resistant strain cell K562R was successfully constructed in vitro. The expression of ITM2A in the resistant strain was significantly lower than that in the sensitive strain(P<0.05). Overexpression of ITM2A in K562R cells increased the sensitivity of K562R cells to imatinib and blocked the cell cycle in G2 phase(P<0.05), but did not affect myeloid differentiation. Mechanistically, up-regulation of ITM2A reduced phosphorylation in ERK signaling (P<0.05). CONCLUSION: The expression of ITM2A was low in patients with drug resistance of CML, and the low expression of ITM2A may be the key factor of imatinib resistance in CML.


Assuntos
Antineoplásicos , Leucemia Mielogênica Crônica BCR-ABL Positiva , Humanos , Antineoplásicos/farmacologia , Apoptose , Resistencia a Medicamentos Antineoplásicos , Mesilato de Imatinib/farmacologia , Mesilato de Imatinib/uso terapêutico , Células K562 , Leucemia Mielogênica Crônica BCR-ABL Positiva/tratamento farmacológico , Transdução de Sinais
14.
J Am Chem Soc ; 145(3): 1924-1935, 2023 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-36571792

RESUMO

High-entropy compounds with extraordinary properties due to the synergistic effect of multiple components have exhibited great potential and attracted extensive attention in various fields, including physics, mechanical property analysis, and energy storage. Achieving universal stability and synthesis of high-entropy compounds with a wide range of components and structures continues to be difficult due to the high complexity of multicomponent mixing. Here, we propose a design strategy with high generality for realizing the stability and synthesis of high-entropy compounds that one metal site like the framework in the compound structures with bimetallic sites stabilizes another site to accommodate different elements. Several typical metal compounds with bimetallic sites, including perovskite hydroxides, layered double hydroxide, spinel sulfide, perovskite fluoride, and spinel oxides, have been synthesized into high-entropy compounds. High-entropy perovskite hydroxides (HEPHs) as representative compounds have been synthesized with a highly wide range of components even a septenary component and exhibit great oxygen evolution activity. Our work provides a design platform to develop more high-entropy compound systems with promising development potential for electrocatalysts.

15.
Adv Mater ; 35(7): e2209290, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36455877

RESUMO

Increasing pursuit of next-generation wearable electronics has put forward the demand of reliable energy devices with high flexibility, durability, and enhanced electrochemical performances. Flexible aqueous zinc-air batteries (FAZABs) have attracted great interests owing to the high energy density, safety, and environmental benignity, for which quasi-solid-state gel polymer electrolytes (QSGPEs) are state-of-the-art electrolytes with high ionic conductivity, flexibility, and resistance to leakage problems of traditional liquid electrolytes. Compared to commonly used PVA-KOH electrolyte with poor electrolyte retention capability and cycling stability, a new type of sulfonate functionalized nanocomposite QSGPE is applied in FAZABs with high ionic conductivity, strong alkaline tolerance, and high zinc anode stability. Notably, the existence of (1) strong anionic sulfonate groups of QSGPEs, contributing to the exposure of preferred Zn (002) plane that is more resistant to zinc dendrite formation, and (2) nano-attapulgite electrolyte additives, beneficial for the enhancement of ionic conductivity, electrolyte uptake, and retention capability, endows a ultralong cycling life of 450 h for the fabricated FAZAB. Furthermore, flexible energy belts and knittable energy wires fabricated with a series/parallel unit of several FAZABs can be used to power various wearable electronics.

16.
Nano Lett ; 22(16): 6492-6500, 2022 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-35950973

RESUMO

High-entropy oxide (HEO) including multiple principal elements possesses great potential for various fields such as basic physics, mechanical properties, energy storage, and catalysis. However, the synthesis method of high-entropy compounds through the traditional heating approach is not conducive to the rapid properties screening, and the current elemental combinations of HEO are also highly limited. Herein, we report a rapid synthesis method for HEO through the Joule-heating of nickel foil with dozens of seconds. High-entropy rocksalt oxides (HERSO) with the new elemental combination, high-entropy spinel oxides (HESO), and high-entropy perovskite oxide (HEPO) have been synthesized through the Joule-heating. The synthesized HERSO with new elemental combinations proves to be a great promotion of OER activity due to the synergy of multiple components and the continuous electronic structure experimentally and theoretically. The demonstrated synthesis approach and the new component combination of HERSO provide a broad platform for the development of high-entropy materials and catalysts.

17.
Small ; 18(33): e2203166, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35871547

RESUMO

Developing wide temperature range flexible solid-state supercapacitors with high volumetric energy density is highly desirable to meet the demands of the rapidly developing field of miniature consumer electronic devices and promote their widespread adoption. Herein, high-quality dense N-doped 3D porous graphene/carbon nanotube (N-3DG/CNTs) hybrid films are prepared and used as the substrate for the growth of Ni-doped MnO2 (Ni-MnO2 ). The integrated and interconnected architecture endows N-3DG/CNTs@Ni-MnO2 composite electrodes' high conductivity and fast ion/electron transport pathway. Subsequently, 2.4 V solid-state supercapacitors are fabricated based on compacted N-3DG/CNTs@Ni-MnO2 positive electrodes, which exhibit an ultrahigh volumetric energy density of 78.88 mWh cm-3 based on the entire device including electrodes, solid-state electrolyte, and packing films, excellent cycling stability up to 10 000 cycles, and a wide operating temperature range from -20 to 70 °C. This work demonstrates a design of flexible solid-state supercapacitors with exceptional volumetric performance capable of operation under extreme conditions.

18.
ACS Appl Mater Interfaces ; 14(22): 25337-25347, 2022 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-35605282

RESUMO

Single-atom catalysts (SACs) have demonstrated catalytic efficacy toward lithium polysulfide conversion in Li-S batteries. However, achieving high-density M-Nx sites with rational design by a simple method is still challenging to date. Herein, an ultrathin porous 3D carbon-supported single-atom catalyst (SACo/NDC) is synthesized with a salt-template strategy via a facile freeze-drying and one-step pyrolysis procedure and serves well as a sulfur host. The well-defined 3D carbon structure can effectively alleviate volume stress and confine polysulfides inside. Moreover, the dispersed Co-Nx sites exhibit strong chemical adsorption function and valid catalytic efficiency to LiPSs redox conversion. As a result, the SACo/NDC cathodes display enhanced long-term cycling stability and better rate capability.

19.
J Am Chem Soc ; 144(7): 3106-3116, 2022 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-35148080

RESUMO

Two-dimensional transition metal dichalcogenides (TMDCs) show great potential as efficient catalysts for Li-CO2 batteries. However, the basal plane engineering on TMDCs toward bifunctional catalysts for Li-CO2 batteries is still poorly understood. In this work, density functional theory calculations reveal that nucleophilic N dopants and electrophilic S vacancies in the ReS2 plane tailor the interactions with Li atoms and C/O atoms in intermediates, respectively. The electrophilic and nucleophilic dual centers show suitable adsorption with all intermediates during discharge and charge, resulting in a small energy barrier for the rate-determining step. Thus, an efficient bifunctional catalyst is produced toward Li-CO2 batteries. As a result, the optimal catalyst achieves an ultrasmall voltage gap of 0.66 V and an ultrahigh energy efficiency of 81.1% at 20 µA cm-2, which is superior to those of previous catalysts under similar conditions. The introduction of electrophilic and nucleophilic dual centers provides new avenues for designing excellent bifunctional catalysts for Li-CO2 batteries.

20.
Adv Mater ; 34(13): e2107053, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35080286

RESUMO

Developing robust and highly active non-precious electrocatalysts for the hydrogen/oxygen evolution reaction (HER/OER) is crucial for the industrialization of hydrogen energy. In this study, a highly active and durable single-atom W-doped NiS0.5 Se0.5 nanosheet @ NiS0.5 Se0.5 nanorod heterostructure (W-NiS0.5 Se0.5 ) electrocatalyst is prepared. W-NiS0.5 Se0.5 exhibits excellent catalytic activity for the HER and OER with ultralow overpotentials (39 and 106 mV for the HER and 171 and 239 mV for the OER at 10 and 100 mA cm-2 , respectively) and excellent long-term durability (500 h), outperforming commercial precious-metal catalysts and many other previously reported transition-metal-based compounds (TMCs). The introduction of single-atom W delocalizes the spin state of Ni, which results in an increase in the Ni d-electron density. This causes the optimization of the adsorption/desorption process of H and a significant reduction in the adsorption free energy of the rate-determining step (O* → OOH*), thus accelerating the thermodynamics and kinetics of the HER and OER. This work provides a rational feasible strategy to design single-atom catalysts for water splitting and to develop advanced TMC electrocatalysts by regulating delocalized spin states.

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