Isomerization of surface functionalized SWCNTs and the critical influence on photoluminescence: static calculations and excited-state dynamics simulations.

Single-walled carbon nanotubes (SWCNTs) functionalized with sparse surface chemical groups are promising for a variety of optical applications such as quantum information and bio-imaging. However, the luminescence efficiencies and stability, two key aspects, undoubtedly govern their practical usage. Herein, we assess the surface migration of oxygen and triazine groups on as-modified SWCNT fragments by adopting transition state theory and explore the de-excitation of oxygen-functionalized SWCNT fragments by performing non-adiabatic excited-state dynamics simulations. According to the predicted moderate or even small reaction barriers, the migration of both oxygen and triazine groups is feasible from an sp3 defect configuration forming an energetically more stable sp2 configuration at moderate or even room temperatures. Such isomerization leads to drastically different light emission capabilities as indicated by the large or zero oscillator strengths. During the dynamics simulations, the lowest excited singlet (S1) state rapidly decays in energy within 20 fs and then fluctuates until the end, providing insights into the emission mechanism of SWCNTs. This study highlights the potential intrinsic limitations of surface-functionalized SWCNTs for luminescence applications.

Co-Doped Ni3V2O8 Nanofibers Achieving d-d Orbital Coupling for Electrocatalytic Oxygen Reduction.

Efficient and robust non-platinum-group metal electrocatalysts for O2 reduction are a prerequisite for practical high-performance fuel cells and metal-air batteries. Herein, we reported an integrated principle of gradient electrospinning and controllable pyrolysis to fabricate various Co-doped Ni3V2O8 nanofibers with high oxygen reduction reaction (ORR) activity. The representative Co1.3Ni1.7V2O8 nanofibers showed outstanding ORR performance in an alkaline solution with a half-wave potential (E1/2) of 0.874 V vs RHE, along with high long-term stability. Furthermore, the introduction of Co could effectively restrain the growth of nanoparticles and change the electronic structure of Ni3V2O8. Control experiments and theoretical calculations demonstrated that upon Co-doping, the hybridization between the 3d orbital for both Co and Ni guaranteed the stable adsorption interaction with O2 over Ni and Co metal centers. Meanwhile, the weakened binding ability of Ni3V2O8 to OH* reduced the ORR free energy. Overall, the synergistic effect of Co and Ni metal cations essentially reflected the origin of ORR activity on the Co-doped Ni3V2O8 nanofibers. This work offers new insights and practical guidance for designing highly active ORR catalysts for electrochemical clean energy conversion and storage.

Sign inversion of surface stress-charge response of bulk nanoporous nickel actuators with different surface states.

The surface stress-charge coefficient, ζ, is a fundamental material parameter and reflects the response of surface stress to the change of superficial charge. The sign and the quantity of ζ play a crucial role in electrochemically induced actuation of nanostructured metals. Here, for the first time, we address the electrochemical actuation and the associated stress-charge coefficients of bulk nanoporous nickel (np-Ni) in both strongly (NaOH) and weakly (NaF) adsorbed electrolytes. The results reveal a normal negative value of ζ for the np-Ni with the clean surface, and unusual positive values of ζ for the oxide-covered surface. Interestingly, the oxidized np-Ni cannot recover the conventional negative value of ζ even in the cathodic potential window. Moreover, the reversible strain amplitude and the involved charge are quite different in distinct potential windows (the same electrolyte) or in different electrolytes (strongly or weakly adsorbed). In addition, density functional theory (DFT) calculations have been performed to understand the electrochemical actuation behaviors of the np-Ni with different surface states. In some aspects, the scenario of the np-Ni indeed differs from that of nanoporous noble metals like Au or Pt. Our findings provide useful information on understanding the electrochemical actuation of nanostructured metals, and novel actuators or sensors could be developed based upon earth-abundant metals like Ni, Co, and so forth.

High-Temperature Liquid-Liquid Phase Transition in Glass-Forming Liquid Pd43Ni20Cu27P10.

Liquid-liquid phase transition (LLPT) is a transition from one liquid state to another with the same composition but distinct structural change, which provides an opportunity to explore the relationships between structural transformation and thermodynamic/kinetic anomalies. Herein the abnormal endothermic LLPT in Pd43Ni20Cu27P10 glass-forming liquid was verified and studied by flash differential scanning calorimetry (FDSC) and ab initio molecular dynamics (AIMD) simulations. The results show that the change of the atomic local structure of the atoms around the Cu-P bond leads to the change in the number of specific clusters <0 2 8 0> and <1 2 5 3>, which leads to the change in the liquid structure. Our findings reveal the structural mechanisms that induce unusual heat-trapping phenomena in liquids and advance the understanding of LLPT.

Clean synthesis of RGO/Mn3O4 nanocomposite with well-dispersed Pd nanoparticles as a high-performance catalyst for hydroquinone oxidation.

In this study, a well-dispersed Pd nanoparticle (NP)-supported RGO/Mn3O4 (G/M/Pd) composite was synthesized by a clean synthetic route, where galvanic replacement reaction simply occurred between Mn3O4 and a palladium salt, thereby avoiding the use of harsh reducing and capping agents. The G/M/Pd composite served as a robust catalyst for the catalytic oxidation of hydroquinone (HQ) to benzoquinone (BQ) with H2O2 in an aqueous solution. Oxidation was completed in only 4 min, with a turnover frequency (TOF) of 3613 h-1; this TOF is one hundred times those of previously reported Pd- and Ag-based catalysts. The superior performance was related to the electronic inductive effect between Mn3O4 and Pd NPs, which was verified by density functional theory calculations. Trapping experiments revealed that the oxidation of HQ was considerably related to the ·OH radicals generated from the decomposition of H2O2. In addition, the influencing factors were further investigated, including catalyst and HQ concentrations, solution pH, solvents, and various inorganic and organic interferences. Moreover, the G/M/Pd catalyst exhibits diverse applications for the catalytic oxidation of HQ derivatives with high TOFs.

Dealloying assisted high-yield growth of surfactant-free <110> highly active Cu-doped CeO2 nanowires for low-temperature CO oxidation.

CeO2 is widely used as a commercial CO oxidation catalyst, but it suffers from high-temperature (>200 °C) complete conversion. Despite enormous efforts made to promote its low-temperature activity by interfacing CuO and CeO2, it is still a long-standing challenge to balance the desired catalytic activity with high-yield preparation. Creating intimate synergistic interfaces between Cu and Ce species and exploring surfactant-free large-scale methods are both critical and challenging. To address these concerns, we synthesized highly active Cu doped CeO2 nanowires for low-temperature CO oxidation, relying on intentionally maneuvering precursor alloy compositions and a high-yield dealloying method. The favorable one-dimensional doping structure inherited from the nanowire bundles of the as-dealloyed precursors, clean surfaces and intimate synergistic effects between Cu and Ce contribute to excellent CO oxidation performances, with 5% room-temperature conversion triggered at 35 °C and 100% conversion at 100 °C. 96% of O2 selectivity at 88 °C in CO preferential oxidation was also obtained. The long-term durability for 24 hours at 100% CO conversion without any decay confirms the robust characteristics of the catalysts. Moreover, this work offers some insights into the reasonable design of alloy precursors to realize property-oriented alloys to nanowires batch transformation for the study of industrial catalysts.

Nanoporous Platinum/(Mn,Al)3O4 Nanosheet Nanocomposites with Synergistically Enhanced Ultrahigh Oxygen Reduction Activity and Excellent Methanol Tolerance.

At present, metal/metal oxide composites are considered as potential oxygen reduction reaction (ORR) catalysts for energy-related applications like fuel cells. Here, we fabricated a high-activity, low Pt loading ORR electrocatalyst composed of nanoporous Pt (np-Pt) in intimate contact with lamellar (Mn,Al)3O4 nanosheet (NS). In comparison to Pt/C (Johnson Matthey), the np-Pt/(Mn,Al)3O4 NS catalyst shows a 11.5-fold enhancement in the mass-normalized ORR activity and much better methanol tolerance because of the metal-support interactions between np-Pt and (Mn,Al)3O4. Furthermore, the combination of electrochemical experiments with theoretical calculations verifies that the ORR on the np-Pt/(Mn,Al)3O4 NS catalyst is a direct 4e- pathway in the alkaline solution. In addition, the electrocatalytic mechanisms have also been rationalized by density functional theory (DFT) calculations.