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1.
Tuning the d-orbital electronic configuration of active sites to achieve well-optimized adsorption strength of oxygen-containing intermediates toward reversible oxygen electrocatalysis is desirable for efficient rechargeable Zn-Air batteries but extremely challenging. Herein, this work proposes to construct a Co@Co3O4 core–shell structure to regulate the d-orbital electronic configuration of Co3O4 for the enhanced bifunctional oxygen electrocatalysis. Theoretical calculations first evidence that electron donation from Co core to Co3O4 shell could downshift the d-band center and simultaneously weak spin state of Co3O4, result in the well-optimized adsorption strength of oxygen-containing intermediates on Co3O4, thus contributing a favor way for oxygen reduction/evolution reaction (ORR/OER) bifunctional catalysis. As a proof-of-concept, the Co@Co3O4 embedded in Co, N co-doped porous carbon derived from thickness controlled 2D metal-organic-framework is designed to realize the structure of computational prediction and further improve the performance. The optimized 15Co@Co3O4/PNC catalyst exhibits the superior bifunctional oxygen electrocatalytic activity with a small potential gap of 0.69 V and a peak power density of 158.5 mW cm−2 in ZABs. Moreover, DFT calculations shows that the more oxygen vacancies on Co3O4 contribute too strong adsorption of oxygen intermediates which limit the bifunctional electrocatalysis, while electron donation in the core–shell structure can alleviate the negative effect and maintain superior bifunctional overpotential.  相似文献   

2.
Unlike single-step reactions, multi-step reactions can be greatly facilitated only if all the intermediate reactions can be catalyzed simultaneously and progressively. Herein, the theoretical analysis and experiments to illustrate the superiority of the cascade oxygen evolution reaction (OER) are conducted. As different OER intermediate reactions demand FexNi1-xOOH with altered Fe/Ni ratios, gradient Fe-doped NiOOH can be an ideal electrocatalyst for the efficient cascade OER in line. Fine controlling of the nucleation sequence of iron and nickel sulfides leads to a FeS2@NiS2 core–shell structure. The activated outward diffusion of Fe dopants results in the gradient Fe/Ni ratios in the FexNi1-xOOH shell, where a cascade OER can happen. Electrochemical tests suggest that the FeS2@NiS2 only needs an overpotential of 237 mV to reach the current density of 10 mA cm−2, with fast reaction kinetics and good stability.  相似文献   

3.
Phase engineering of nanomaterials (PEN) offers a promising route to rationally tune the physicochemical properties of nanomaterials and further enhance their performance in various applications. However, it remains a great challenge to construct well-defined crystalline@amorphous core–shell heterostructured nanomaterials with the same chemical components. Herein, the synthesis of binary (Pd-P) crystalline@amorphous heterostructured nanoplates using Cu3−χP nanoplates as templates, via cation exchange, is reported. The obtained nanoplate possesses a crystalline core and an amorphous shell with the same elemental components, referred to as c-Pd-P@a-Pd-P. Moreover, the obtained c-Pd-P@a-Pd-P nanoplates can serve as templates to be further alloyed with Ni, forming ternary (Pd-Ni-P) crystalline@amorphous heterostructured nanoplates, referred to as c-Pd-Ni-P@a-Pd-Ni-P. The atomic content of Ni in the c-Pd-Ni-P@a-Pd-Ni-P nanoplates can be tuned in the range from 9.47 to 38.61 at%. When used as a catalyst, the c-Pd-Ni-P@a-Pd-Ni-P nanoplates with 9.47 at% Ni exhibit excellent electrocatalytic activity toward ethanol oxidation, showing a high mass current density up to 3.05 A mgPd−1, which is 4.5 times that of the commercial Pd/C catalyst (0.68 A mgPd−1).  相似文献   

4.
Developing highly-efficient non-noble-metal electrocatalysts for water splitting is crucial for the development of clean and reversible hydrogen energy. Introducing lattice strain is an effective strategy to develop efficient electrocatalysts. However, lattice strain is typically co-created with heterostructure, vacancy, or substrate effects, which complicate the identification of the strain-activity correlation. Herein, a series of lattice-strained homogeneous NiSxSe1−x nanosheets@nanorods hybrids are designed and synthesized by a facile strategy. The NiS0.5Se0.5 with ≈2.7% lattice strain exhibits outstanding activity for hydrogen and oxygen evolution reaction (HER/OER), affording low overpotentials of 70 and 257 mV at 10 mA cm−2, respectively, as well as excellent long-term durability even at a large current density of 100 mA cm−2 (300 h), significantly superior to other benchmarks and the precious metal catalysts. Experimental and theoretical calculation results reveal that the generated lattice strain decreases the metal d-orbital overlap, leading to a narrower bandwidth and a closer d-band center toward the Fermi level. Thus, NiS0.5Se0.5 possesses favorable H* adsorption kinetics for HER and lower energy barriers for OER. This work provides a new insight to regulate the lattice strain of advanced catalyst materials and further improve the performance of energy conversion technologies.  相似文献   

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Developing efficient and robust metal–nitrogen–carbon electrocatalysts for oxygen reduction reaction (ORR) is of great significance for the application of hydrogen–oxygen fuel cells and metal–air batteries. Herein, a coordination engineering strategy is developed to improve the ORR kinetics and stability of cobalt–nitrogen–carbon (Co–N–C) electrocatalysts by grafting the oxygen-rich graphene quantum dots (GQDs) onto the zeolite imidazole frameworks (ZIFs) precursors. The optimized oxygen-rich GQDs-functionalized Co–N–C (G-CoNOC) electrocatalyst demonstrates an increased mass activity, nearly two times higher than that of pristine defective Co–N–C electrocatalyst, and retains a stability of 90.0% after 200 h, even superior to the commercial Pt/C. Comprehensive investigations demonstrate that the GQDs coordination can not only decrease carbon defects of Co–N–C electrocatalysts, improving the electron transfer efficiency and resistance to the destructive free radicals from H2O2, but also optimize the electronic structure of atomic Co active site to achieve a desired adsorption energy of OOH, leading to enhanced ORR kinetics and stability by promoting further H2O2 reduction, as confirmed by theoretical calculations and experimental results. Such a coordination engineering strategy provides a new perspective for the development of highly active noble-metal-free electrocatalysts for ORR.  相似文献   

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The fabrication of low-cost, effective, and highly integrated nanostructured materials through simple and reproducible methods for high-energy-density supercapacitors is highly desirable. Herein, an activated carbon cloth (ACC) is designed as the functional scaffold for supercapacitors and treated hydrothermally to deposit NiCo nanoneedles working as internal core, followed by a dip-dry coating of NiOOH nanoflakes core–shell and uniform hydrothermal deposition of CoMoO4 nanosheets serving as an external shell. The structured core–shell heterostructure ACC@NiCo@NiOOH@CoMoO4 electrode resulted in exceptional specific areal capacitance of 2920 mF cm−2 and exceptional cycling stability for 10 000 cycles. Moreover, the fabricated electrode is developed into an asymmetric supercapacitor which demonstrates excellent areal capacitance, energy density, and power density within the broad potential window of 1.7 V with a cycling life of 92.4% after 10 000 charge–discharge cycles, which reflects excellent cycle life. The distinctive core–shell structure, highly conductive substrate, and synergetic effect of coated material results in more electrochemical active sites and flanges for effective electrons and ion transportation. This unique technique provides a new perspective for cost-efficient supercapacitor applications.  相似文献   

10.
Electrocatalysis is a highly promising technology widely used in clean energy conversion. There is a continuing need to develop advanced electrocatalysts to catalyze the critical electrochemical reactions. Integrating metal active species, including various metal nanostructures (NSs) and atomically dispersed metal sites (ADMSs), into metal–organic frameworks (MOFs) leads to the formation of promising heterogeneous electrocatalysts that take advantage of both components. Among them, MOFs can provide support and protection for the active sites on guest metals, and the resulting host-guest interactions can synergistically enhance the electrocatalytic performance. In this review, three key concerns on MOF-metal heterogeneous electrocatalysts regarding the catalytic sites, conductivity, and catalytic stability are first presented. Then, rational integration strategies of MOFs and metals, including the integration of metal NSs via surface anchoring, space confining, and MOF coating, as well as the integration of ADMSs either with the metal nodes/linkers or within the pores of MOFs, along with their recent progress on synergistic cooperation for specific electrochemical reactions are summarized. Finally, current challenges and possible solutions in applying these increasingly concerned electrocatalysts are also provided.  相似文献   

11.
Nanowires (NWs) hold great potential in advanced thermoelectrics due to their reduced dimensions and low-dimensional electronic character. However, unfavorable links between electrical and thermal conductivity in state-of-the-art unpassivated NWs have, so far, prevented the full exploitation of their distinct advantages. A promising model system for a surface-passivated one-dimensional (1D)-quantum confined NW thermoelectric is developed that enables simultaneously the observation of enhanced thermopower via quantum oscillations in the thermoelectric transport and a strong reduction in thermal conductivity induced by the core–shell heterostructure. High-mobility modulation-doped GaAs/AlGaAs core–shell NWs with thin (sub-40 nm) GaAs NW core channel are employed, where the electrical and thermoelectric transport is characterized on the same exact 1D-channel. 1D-sub-band transport at low temperature is verified by a discrete stepwise increase in the conductance, which coincided with strong oscillations in the corresponding Seebeck voltage that decay with increasing sub-band number. Peak Seebeck coefficients as high as ≈65–85 µV K−1 are observed for the lowest sub-bands, resulting in equivalent thermopower of S2σ ≈ 60 µW m−1 K−2 and S2G ≈ 0.06 pW K−2 within a single sub-band. Remarkably, these core–shell NW heterostructures also exhibit thermal conductivities as low as ≈3 W m−1 K−1, about one order of magnitude lower than state-of-the-art unpassivated GaAs NWs.  相似文献   

12.
Zinc-air batteries(ZABs)hold tremendous promise for clean and efficient energy storage with the merits of high theoretical energy density and environmental friendliness.However,the performance of practical ZABs is still unsatisfactory because of the inevitably decreased activity of electrocatalysts when assembly into a thick electrode with high mass loading.Herein,we report a hierarchical electrocatalyst based on carbon microtube@nanotube core-shell nanostructure(CMT@CNT),which demonstrates superior electrocatalytic activity for oxygen reduction reaction and oxygen evolution reaction with a small potential gap of 0.678 V.Remarkably,when being employed as air-cathode in ZAB,the CMT@CNT presents an excellent performance with a high power density(160.6 mW cm^−2),specific capacity(781.7 mAhgZn^−1)as well as long cycle stability(117 h,351 cycles).Moreover,the ZAB performance of CMT@CNT is maintained well even under high mass loading(3 mg cm−2,three times as much as traditional usage),which could afford high power density and energy density for advanced electronic equipment.We believe that this work is promising for the rational design of hierarchical structured electrocatalysts for advanced metal-air batteries.  相似文献   

13.
In this work, Fe3O4–ZnO core–shell nanoparticles have been successfully synthesized using a simple two-step co-precipitation method. In this regard, Fe3O4 (magnetite) and ZnO (zincite) nanoparticles (NPs) were synthesized separately. Then, the surface of the Fe3O4 NPs was modified with trisodium citrate in order to improve the attachment of ZnO NPs to the surface of Fe3O4 NPs. Afterwards, the modified magnetite NPs were coated with ZnO NPs. Moreover, the influence of the core to shell molar ratio on the structural and magnetic properties of the core–shell NPs has been investigated. The prepared nanoparticles have been characterized utilizing transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and vibrating sample magnetometer (VSM). The results of XRD indicate that Fe3O4 NPs with inverse spinel phase were formed. The results of VSM imply that the Fe3O4–ZnO core–shell NPs are superparamagnetic. The saturation magnetization of prepared Fe3O4 NPs is 54.24 emu/g and it decreases intensively down to 29.88, 10.51 and 5.75 emu/g, after ZnO coating with various ratios of core to shell as 1:1, 1:10 and 1:20, respectively. This reduction is attributed to core–shell interface effects and shielding. TEM images and XRD results imply that ZnO-coated magnetite NPs are formed. According to the TEM images, the estimated average size for most of core–shell NPs is about 12 nm.  相似文献   

14.
Nanostructures derived from zeolitic-imidazole frameworks (ZIFs) gain much interest in bifunctional oxygen electrocatalysis. However, they are not satisfied well for long-life rechargeable zinc–air batteries due to the limited single particle morphology. Herein, the preparation of an interconnected macroporous carbon matrix with a well-defined 3D architecture by the pyrolysis of silica templated ZIF-67 assemblies is reported. The matrix catalyst assembled zinc–air battery exhibits a high power density of 221.1 mW cm−2 as well as excellent stability during 500 discharging/charging cycles, surpassing that of a commercial Pt/C assembled battery. The synergistic effect from the interconnected macroporous structure together with abundant cobalt–nitrogen–carbon active sites justify the excellent electrocatalytic activity and battery performance. Considering the advanced nanostructures and performance, the as-synthesized hybrid would be promising for rechargeable zinc–air batteries and other energy technologies. This work may also provide significant concept in the view of electrocatalysis design for long-life battery.  相似文献   

15.
Heteroepitaxial modification of nanomaterials has become a powerful means to create novel functionalities for various applications. One of the most elementary factors in heteroepitaxial nanostructures is the misfit strain arising from mismatched lattices of the constituent parts. Misfit strain not only dictates epitaxy kinetics for diversifying nanocrystal morphologies but also provides rational control over materials properties. In recent years, advances in chemical synthesis along with the rapid development of electron microscopy and X-ray diffraction techniques have enabled a substantial understanding of strain-related processes, which offers theoretical foundation and experimental guidance for researchers to refine heteroepitaxial nanostructures and their properties. Herein, recent investigations on heterogeneous core–shell nanocrystals containing misfit strains are summarized, with a focus on the mechanistic understanding of strain and strain-induced effects such as tuning the epitaxial habit, modulating the optical emission, and enhancing the catalytic activity and magnetic coercivity.  相似文献   

16.
The vigorous development of efficient platinum group metal-free catalysts is considerably important to facilitate the universal application of proton exchange membrane fuel cells. Although nitrogen-coordinated atomic iron intercalated in carbon matrix (Fe–N–C) catalysts exhibit promising catalytic activity, the performance in fuel cells, especially the short lifetime, remains an obstacle. Herein, a highly-active Fe–N–C catalyst with a power density of >1 w cm-2 and prolonged discharge stability with a current density of 357 mA cm-2 after 40 h of constant voltage discharge at 0.7 V in H2–O2 fuel cells using a controllable and efficient N–C coating strategy is developed. It is clarified that a thicker N–C coating may be more favorable to enhance the stability of Fe–N–C catalysts at the expense of their catalytic activity. The stability enhancement mechanism of the N–C coating strategy is proven to be the synergistic effect of reduced carbon corrosion and iron loss. It is believed that these findings can contribute to the development of Fe–N–C catalysts with high activity and long lifetimes.  相似文献   

17.
Developing advanced luminescent materials and techniques is of significant importance for anti-counterfeiting applications, and remains a huge challenge. In this work, a new and efficient approach for achieving efficient dual-mode luminescence with tunable color outputs via Gd3+-mediated interfacial energy transfer, Ce3+-assisted cross-relaxation, and core–shell nanostructuring strategy is reported. The introduction of Ce3+ into the inner core not only serves the regulation of upconversion emission, but also facilitates the ultraviolet photon harvesting and subsequent energy transfer to downshifting (DS) activators in the outer shell layer. Furthermore, the construction of the core@shell nanoarchitecture enables the spatial separation of upconverting activators and DS centers, which greatly suppresses their adverse cross-relaxation processes. Consequently, efficient and multicolor-tunable dual-mode emissions can be simultaneously observed in the pre-designed NaGdF4:Yb/Ho/Ce@NaYF4:X (X = Eu, Tb, Sm, Dy) core–shell nanostructures under 254 nm ultraviolet light and 980 nm laser excitation. The proof-of-concept experiment demonstrates that 2D-encoded patterns based on dual-mode emitting nanomaterials are very promising for anti-counterfeiting applications. It is believed that this preliminary study will advance the development of the fluorescent materials for potential applications in anti-counterfeiting and optical multiplexing.  相似文献   

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Multivariate metal–organic framework (MOF) is an ideal electrocatalytic material due to the synergistic effect of multiple metal active sites. In this study, a series of ternary M-NiMOF (M = Co, Cu) through a simple self-templated strategy that the Co/Cu MOF isomorphically grows in situ on the surface of NiMOF is designed. Owing to the electron rearrange of adjacent metals, the ternary CoCu-NiMOFs demonstrate the improved intrinsic electrocatalytic activity. At optimized conditions, the ternary Co3Cu-Ni2MOFs nanosheets give the excellent oxygen evolution reaction (OER) performance of current density of 10 mA cm−2 at low overpotential of 288 mV with a Tafel slope of 87 mV dec−1, which is superior to that of bimetallic nanosheet and ternary microflowers. The low free energy change of potential-determining step identifies that the OER process is favorable at Cu–Co concerted sites along with strong synergistic effect of Ni nodes. Partially oxidized metal sites also reduce the electron density, thus accelerating the OER catalytic rate. The self-templated strategy provides a universal tool to design multivariate MOF electrocatalysts for highly efficient energy transduction.  相似文献   

20.
Energetic materials, including explosives, pyrotechnics, and propellants, are widely used in mining, demolition, automobile airbags, fireworks, ordnance, and space technology. Nanoenergetic materials (nEMs) have a high reaction rate and high energy density, which are both adjustable to a large extent. Structural control over nEMs to achieve improved performance and multifunctionality leads to a fascinating research area, namely, nanostructured energetic materials. Among them, core–shell structured nEMs have gained considerable attention due to their improved material properties and combined multiple functionalities. Various nEMs with core–shell structures have been developed through diverse synthesis routes, among which core–shell structured nEMs associated with explosives and metastable intermolecular composites (MICs) are extensively studied due to their good tunability and wide applications, as well as excellent energetic (e.g., enhanced heat release and combustion) and/or mechanical properties. Herein, the preparation methods and fundamental properties of the abovementioned kinds of core–shell structured nEMs are summarized and the reasons behind the satisfactory performance clarified, based on which suggestions regarding possible future research directions are proposed.  相似文献   

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