RESUMO
Rechargeable potassium ion batteries have long been regarded as one alternative to conventional lithium ion batteries because of their resource sustainability and cost advantages. However, the compatibility between anodes and electrolytes remains to be resolved, impeding their commercial adoption. In this work, the K-ion storage properties of Bi nanoparticles encapsulated in N-doped carbon nanocomposites have been examined in two typical electrolyte solutions, which show a significant effect on potassium insertion/removal processes. In a KFSI-based electrolyte, the N-C@Bi nanocomposites exhibit a high specific capacity of 255.2 mAh g-1 at 0.5 A g-1, which remains at 245.6 mAh g-1 after 50 cycles, corresponding to a high capacity retention rate of 96.24%. In a KPF6-based electrolyte, the N-C@Bi nanocomposites show a specific capacity of 209.0 mAh g-1, which remains at 71.5 mAh g-1 after 50 cycles, corresponding to an inferior capacity retention rate of only 34.21%. Post-investigations reveal the formation of a KF interphase derived from salt decomposition and an intact rod-like morphology after cycling in K2 electrolytes, which are responsible for better K-ion storage properties.
RESUMO
The heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although the dissimilar metal identification and essential mechanism that dominate the kinetics remain unclear. It is presented that d-p orbital hybridization between the metal and electrolyte ions can be utilized as a descriptor for understanding the redox kinetics. Herein, a series of Co, Fe and Cu heteroatoms are respectively introduced into Ni3Se4 cathodes, among them, only the moderate Co-substituted Ni3Se4 can hold the optimal d-p orbital hybridization resulted from the formed more unoccupied antibonding states π*. It inevitably enhances the interfacial charge transfer and ensures the balanced OH- adsorption-desorption to accelerate the redox kinetics validated by the lowest reaction barrier (0.59â eV, matching well with the theoretical calculations). Coupling with the lower OH- diffusion energy barrier, the prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even the current density increases by 200â times), and an assembled HSC also presents high energy/power density. This work establishes the principles for determining heteroatoms and deciphers the underlying effects of the heteroatom substitution on improving redox kinetics and the rate performance of battery-type electrodes from a novel perspective of orbital-scale manipulation.
RESUMO
Photocatalytic H2 production is envisioned as a promising pillar of sustainable energy conversion system to address the energy crisis and environmental issues but still challenging. Herein, a strategy is proposed to design a dual-metal cocatalysts consisting of Pt nanoclusters (Pt NCs) and In nanoparticles (In NPs) anchored on polymeric carbon nitride (Pt-In/CN) for boosting photocatalytic water splitting. As expected, the designed Pt-In/CN photocatalyst exhibits an impressive H2 production rate of 6.49 mmol·h-1·g-1 with an apparent quantum yield (AQY) of 33.56 % at 400 nm, which is 2.8- and 11.2-fold higher than those of the Pt/CN and In/CN, respectively. Combining experimental characterization with theoretical calculation demonstrates the synergistic mechanisms underpinning the enhanced photocatalytic activity. The Pt NCs and In NPs serve as photogenerated electron and hole trapping sites, respectively, which achieves the spatial separation of charge carriers and induces the polarized surface charge distribution, thus fostering optimal adsorption behavior of intermediates. More importantly, the p-block In NPs modulate the electronic microenvironment of Pt NCs to attenuate the adsorption behavior of H* intermediates for accelerated H2 evolution kinetics. This work unveils a versatile strategy to regulate the electronic structures of dual-metal sites with synergy by establishing charge transfer mechanism for dual-metal cocatalysts.
RESUMO
Under-sampling is an advantageous way for lowering sampling circuit complexity in phase laser ranging while maintaining high modulated frequency operation. Improving the accuracy of the ranging system is the aim of the proposed selection criteria with involved under-sampling parameters. These parameters include signal frequency, sampling frequency, and calculation points. Setting the number of one periodic sampling points to be an integer power of 2 (p o w e r=2-6) optimizes the accuracy in integral periodic sampling. Levering up calculated periods with limited calculated points and averaging the calculated phase by employing the corresponding average parameter can both enhance accuracy in non-integral periodic sampling. These criteria are verified through derivation and simulation and are applied to the ranging system. The experimental results demonstrate that, by applying these selection criteria, the phase detection accuracy in the under-sampling ranging system can be potently improved without any pre-processing or algorithmic refinement.
RESUMO
Bi2Te3-based alloys, as the sole commercial thermoelectric (TE) material, play an irreplaceable role in the thermoelectric field. However, the low TE efficiency, poor mechanical properties, and high cost have limited its large-scale applications. Here, high-performance p-type Bi2Te3-based materials were successfully prepared by ball milling and hot pressing. The optimized p-type Bi0.55Sb1.45Te3 + 2.5 wt % Bi shows a peak zT value of 1.45 at 360 K, and the average zT value of up to 1.24 at 300-480 K, which is completely comparable with previously reported Bi2Te3-based alloys with excellent performance. Such performance mainly results from the enhanced electrical conductivity and decreased lattice thermal conductivity via regulating carrier and phonon transport. Furthermore, this material shows good mechanical properties, in which the Vickers hardness and compressive strength are up to 0.95 GPa and 94.6 MPa, respectively. Overall, both the thermoelectric and mechanical performance of the materials fabricated by our processing technology are quite competitive. This may enlighten researchers concentrating on Bi2Te3-based alloys, thus further promoting their industrial applications.
RESUMO
It is a challenge to regulate charge separation dynamics and redox reaction kinetics at the atomic level to synergistically boost photocatalytic hydrogen (H2) evolution. Herein, a robust Ni-doped CdS (Ni-CdS) photocatalyst is synthesized by incorporating highly dispersed Ni atoms into the CdS lattice in substitution for Cd atoms. Combined characterizations with theoretical analysis indicate that local lattice distortion and S-vacancy of Ni-CdS induced by Ni incorporation lead to an increased dipole moment and enhanced spin-polarized electric field, which promotes the separation and transfer of photoinduced carriers. In this contribution, charge redistribution caused by enhanced internal electric field results in the downshift of the S p-band center, which is conducive to the desorption of intermediate H* for boosting the H2 evolution reaction. Accordingly, the Ni-CdS photocatalyst shows a remarkably improved photocatalytic performance with an H2 evolution rate of 20.28 mmol g-1 h-1 under visible-light irradiation, which is 5.58 times higher than that of pristine CdS. This work supplied an insightful understanding that the enhanced polarization electric field governs the p-band center for efficient photocatalytic H2 evolution activity.
RESUMO
The rupture of a micro/nano container can trigger the release of repair agents and provides the coating with a self-healing and anti-corrosion effect. However, the defect and inhomogeneity of the coating, produced by the rupture of the micro/nano container, may weaken its anti-corrosion performance. This study reports a rare protection mechanism, which optimizes the space occupying of zirconium phosphate, and the de-doping peculiarity of polyaniline without the rupture of the micro/nano container. Polyaniline/α-zirconium phosphate composites were constructed through in situ oxidation polymerization. Repair agents were added in the form of doped acids. According to the different repair agents in polyaniline/α-zirconium phosphate composites (citric ion, tartaric ion and phytic ion), the performance and protection mechanism of the composites were researched. Polyaniline/α-zirconium phosphate coating (with phytic ion) shows an excellent self-healing anti-corrosive effect, due to the large spatial structure and abundant chelating groups of the precipitation inhibitor. Considering the anti-corrosive application, the developed polyaniline/α-zirconium phosphate composite has a far-reaching influence on marine development.