Kunpeng Xie

Spinel Mn–Co Oxide in N-Doped Carbon Nanotubes as a Bifunctional Electrocatalyst Synthesized by Oxidative Cutting

The notorious instability of non-precious-metal catalysts for oxygen reduction and evolution is by far the single unresolved impediment for their practical applications. We have designed highly stable and active bifunctional catalysts for reversible oxygen electrodes by oxidative thermal scission, where we concurrently rupture nitrogen-doped carbon nanotubes and oxidize Co and Mn nanoparticles buried inside them to form spinel Mn-Co oxide nanoparticles partially embedded in the nanotubes. Impressively high dual activity for oxygen reduction and evolution is achieved using these catalysts, surpassing those of Pt/C, RuO2, and IrO2 and thus raising the prospect of functional low-cost, non-precious-metal bifunctional catalysts in metal-air batteries and reversible fuel cells, among others, for a sustainable and green energy future.

Hollow and yolk-shell iron oxide nanostructures on few-layer graphene in Li-ion batteries.

We report a simple and template-free strategy for the synthesis of hollow and yolk-shell iron oxide (FeOx) nanostructures sandwiched between few-layer graphene (FLG) sheets. The morphology and microstructure of this material are characterized in detail by X-ray diffraction, X-ray absorption near-edge structure, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning and transmission electron microscopy. Its properties are evaluated as negative electrode material for Li-ion batteries and compared with those of solid FeOx/FLG and two commercial iron oxides. In all cases, the content of carbon in the electrode has a great influence on the performance. The use of pristine FLG improves the capacity retention and further enhancement is achieved with the hollow structure. For a low carbon loading of 18 wt. %, the presence of metallic iron in the hollow and yolk-shell FeOx/FLG composite significantly enhances the capacity retention, albeit with a relatively lower initial reversible capacity, retaining above 97% after 120 cycles at 1000 mA g(-1) in the voltage range of 0.1-3.0 V.

Purified oxygen- and nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Abstract Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH 3 post-treatment of OCNTs. Temperature-programmed desorption, N 2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.

Co3O4–MnO2–CNT Hybrids Synthesized by HNO3 Vapor Oxidation of Catalytically Grown CNTs as OER Electrocatalysts

An efficient two‐step gas‐phase method was developed for the synthesis of Co3O4–MnO2–CNT hybrids used as electrocatalysts in the oxygen evolution reaction (OER). Spinel Co–Mn oxide was used for the catalytic growth of multiwalled carbon nanotubes (CNTs) and the amount of metal species remaining in the CNTs was adjusted by varying the growth time. Gas‐phase treatment in HNO3 vapor at 200 °C was performed to 1) open the CNTs, 2) oxidize encapsulated Co nanoparticles to Co3O4 as well as MnO nanoparticles to MnO2, and 3) to create oxygen functional groups on carbon. The hybrid demonstrated excellent OER activity and stability up to 37.5 h under alkaline conditions, with longer exposure to HNO3 vapor up to 72 h beneficial for improved electrocatalytic properties. The excellent OER performance can be assigned to the high oxidation states of the oxide nanoparticles, the strong electrical coupling between these oxides and the CNTs as well as favorable surface properties rendering the hybrids a promising alternative to noble metal based OER catalysts.

Low temperature Hydrogen Reduction of High Surface Area Anatase and Anatase/β-TiO2 for High-Charging-Rate Batteries

There are several strategies to improve the electrochemical performance of TiO2 as negative electrode material for Li-ion batteries. Introducing oxygen vacancies through hydrogen reduction leads to an enhancement in electrical conductivity. However, this strategy does not improve the low lithium-ion mobility. Herein, we show that by decreasing the temperature of hydrogen annealing the improved lithium-ion mobility of high-surface-area TiO2 and β-TiO2 can be combined with the enhanced electrical conductivity of oxygen deficiencies. Annealing at only 275-300 °C in pure hydrogen atmosphere successfully creates oxygen vacancies in TiO2, as confirmed by UV/Vis spectroscopy, whereas the temperature is low enough to maintain a high specific surface area and prevent β-to-anatase phase transformation. The hydrogen reduction of high-surface-area anatase or anatase/β-TiO2 at these temperatures leads to improvements in the performance, achieving charge capacities of 142 or 152 mAh g(-1) at 10C, respectively.

Ammonia Desorption Peaks Can Be Assigned to Different Copper Sites in Cu/SSZ-13

The purpose of this study is to attribute NH3-TPD peaks observed over Cu/SSZ-13 catalysts to different catalytic sites. This is done by comparing a large number of copper loadings, especially below 40% ion exchange, to be able to see effects relevant to sites in both 6-membered and 8-membered rings. We found that intermediate (200–300 °C) and high (400–500 °C) temperature NH3-TPD peaks followed similar trends to the copper species in 6-membered and 8-membered rings respectively, as seen by H2-TPR and NO-DRIFTS. Thus we propose that these two TPD peaks represent ammonia stored on H and Cu sites in 6 and 8-membered rings, respectively. This assignment is further supported by the finding that the intermediate and high temperature NH3-TPD peaks of samples with different Si/Al ratios also follow the same trend. Moreover, we observe that the activation energy for ammonia oxidation is significantly lower for Cu in 6MR compared to Cu in 8MR rings.Graphical Abstract

New Understanding on Photocatalytic Mechanism of Nitrogen-Doped Graphene Quantum Dots-Decorated BiVO4 Nanojunction Photocatalysts

Bismuth vanadate (BiVO4) is a promising candidate as a visible-light-driven photocatalyst in the aspect of practical applications. To investigate the origin of active species from BiVO4 and understand the influence of the variations of the photocatalytic process, comparative studies on zero-dimensional nitrogen-doped graphene quantum dot (NGQD)-decorated BiVO4 have been carried out for methylene blue photodegradation. It was found that the hydroxyl group-rich NGQD surface and the established heterojunction structure between NGQDs and BiVO4 were greatly beneficial for the conversion of the •OH radical. With NGQD decoration, the dominant oxidant species for NGQDs/BiVO4 were confirmed to be •OH and H2O2, rather than holes originating from the valence band of unmodified BiVO4. The synergistic photocatalytic mechanism with respect to the interfacial charge transport and the conversion of active species was proposed. The achievement of the controllable active species significantly altering the activity may be applied for different photocatalytic reactions.

Tuning Ag morphology on TiO2 nanotube arrays by pulse reverse current deposition for enhanced plasmon-driven visible-light response

TiO2 nanotube arrays (NTAs) decorated with controllable Ag particles were prepared by pulse reverse current deposition in AgNO3/NaNO3 aqueous solution, aiming to improve the photoelectrochemical properties of TiO2 NTA electrode in visible-light region. By tuning the pulse current density and deposited charge density, a controllable synthesis of Ag structures was achieved. Excellent photocurrent responses of TiO2 NTAs in UV and visible light regions were achieved by depositing Ag nanorods and nanoparticles, which was attributed to highly efficient charge separation by the Schottky junction at the Ag/TiO2 interface and localized surface plasmon resonance effect of Ag nanostructures.Graphical Abstract