2D VS2 @MXene Based Zinc Ion Batteries with SPANI-Contained Electrolyte Enables Dendrite-Free Anode for Stable Cycling.

Regarded as one of the popular cathode materials in aqueous zinc ion batteries (ZIBs), VS2 has unsatisfied cycling stability and relatively low capacity owing to its poor conductivity and low mechanical properties. To this regard, compositing VS2 with high-conductive 2D transition metal carbide (MXene) has been an effective method recently. However, the Zn dendrite on the anode electrode derived from the uncontrollable sluggish migration of solvated Zn2+ /H2 O ions seriously threatens the application safety of ZIB batteries. To effectively regulate the diffusion of zinc ions, in this work a conductive polymeric electrolyte of sulfonated polyaniline (SPANI) is added in the electrolyte solution. Under the Zn2+ /SPANI interactions confirmed by X-ray diffraction, Raman, and zeta potential experiments, the Zn2+ /H2 O combination is weakened, and the deposition rate of Zn2+ is increased evaluated by the galvanostatic intermittent titration technique. Theoretical simulation shows that the electrostatic shielding by SPANI combining Zn2- at the zinc/electrolyte interface has important contribution to the significant suppression of Zn dendrite. Accordingly, the fabricated VS2 @MXene||ZnSO4 +SPANI||Zn battery shows high capacity (368.0 mAh g-1 at 0.1 A g-1 ), which remains 96% after 5000 cyclic charge-discharge operations. This work develops an available strategic idea for suppressing growth of metallic dendrites to improve the ZIB performances.

Water-Phase Lateral Interconnecting Quantum Dots as Free-Floating 2D Film Assembled by Hydrogen-Bonding Interactions to Acquire Excellent Electrocatalytic Activity.

Supramolecular self-assembly of nanoparticles in two orthogonal directions would potentially allow one to fabricate nanomaterials with fascinating properties. In this study of a hydrothermal polycondensation of melamine/cyanuric acid, graphitic carbon nitride-based quantum dots (CNQD, ∼2 nm) are in situ arranged along two orthogonal directions through lateral hydrogen bonding, and free-floating two-dimensional hydrogen-bonded films of CNQD (2D CNQD) are built. On the basis of the universality of this hydrothermal in situ supramolecular self-assembly technique, 2D films linked by other quantum dots such as sulfur-doped graphitic carbon nitride and CdTe are also constructed. With the benefits of stimuli responsiveness and the reversibility of hydrogen bonds, controllable assembly/disassembly of the 2D CNQD film is feasibly achieved by external stimuli such as inletting CO2/N2, which endows the assembled 2D CNQD films optimal electrochemical superiorities of both 2D film and zero-dimensional (0D) quantum dots. Accordingly, the 2D CNQD film delivers a high bifunctional activity in both a nitrogen reduction reaction (NRR) and an oxygen evolution reaction (OER). Especially in NRR, it exhibits the high yield rate of NH3 reaching 75.07 µg h-1 mg-1 at -0.85 V versus reversible hydrogen electrode at ambient condition. Strikingly, the power density of the rechargeable Zn-N2 battery using 2D CNQD film as cathode reaches 31.94 mW cm-2, outperforming the majority of Zn-N2 batteries. Density functional theory calculations proved the promoted adsorption of N2 and stabilized NRR intermediates on 2D CNQD cooperated by multiply hydrogen-bonding interactions are the main reasons for the excellent NRR electrocatalytic performances. This work hints that hydrothermal in situ supramolecular self-assembly is a feasible and direct way to integrate 0D quantum dots into 2D directional arrays, and the hydrogen bond that interlinks enables this free-floating 2D structure to maintain the electrochemical superiority of both 0D and 2D structures.

Enhanced Electrochemical Performance by Strongly Anchoring Highly Crystalline Polyaniline on Multiwalled Carbon Nanotubes.

Highly crystalline polyaniline (PANI) was strongly anchored on a multiwalled carbon nanotube (MWNT) surface, slowly grown from a controlled isothermal crystallization method utilizing π-π interactions. The crystalline PANI particles are approximately 10-38 nm thick, and the space between them varies from near 0 to 55 nm as reaction conditions vary. The highly crystalline nanohybrid (CNH) showed electrochemical performance enhancement compared with that of neat MWNTs, PANI, and the reference hybrid synthesized from chemical polymerization. The specific capacitance (SC) of CNHs was 726 F g-1 coupled with an excellent rate capability. Moreover, the strong combination between PANI and MWNTs as well as the crystalline structure in PANI improved the bulk conductivity, the interfacial charge transportation, and the cycling stability of the CNHs. The SC value of the CNHs remained almost unchanged upon 1000 charge-discharge cycles, followed by just a slight decline of 2.6% after 10 000 cycle tests. X-ray diffraction data shows the SC decline mainly resulted from the structural variation of crystalline PANI. Furthermore, the resulting CNHs showed significant electrocatalytic behavior toward H2O2 and exhibited a low detection limit of 4.4 µM due to the enhanced electron transportation between MWNTs and PANI. The reported method opens a gateway to design high-performance MWNT/PANI hybrids for use in electrochemical sensors, fuel cells, and energy-storage related devices.

Enhanced Electronic Communication and Electrochemical Sensitivity Benefiting from the Cooperation of Quadruple Hydrogen Bonding and π-π Interactions in Graphene/Multi-Walled Carbon Nanotube Hybrids.

By designing a molecule labeled as UPPY with both ureidopyrimidinone (UP) and pyrene (PY) units, the supramolecular self-assembly of multiwalled carbon nanotube (MWNT) and reduced graphene oxide (rGO) was driven by the UP quadruple hydrogen-bonding and PY-based π-π interactions to form a novel hybrid of rGO-UPPY-MWNT in which the morphology of rGO-wrapped MWNT was found. Bridged by the two kinds of noncovalent bonding, enhanced electronic communication occurred in rGO-UPPY-MWNT. Also, under the cooperation of UP quadruple hydrogen-bonding and PY-based π-π interactions, higher electrical conductivity and better charge transfer were observed for rGO-UPPY-MWNT, compared with the rGO-MWNT composite without such noncovalent bonds, and that with just single PY-based π-π interaction (rGO-PY-MWNT) or UP quadruple hydrogen bond (rGO-UP-MWNT). Specifically, the electrical conductivity of rGO-PY-MWNT hybrids was increased approximately sevenfold, and the interfacial charge transfer resistance was nearly decreased by 1 order of magnitude compared with rGO-MWNT, rGO-UP-MWNT, and rGO-PY-MWNT. Resulting from its excellent electrical conductivity and charge transfer properties, the rGO-UPPY-MWNT modified electrode exhibited enhanced electrochemical activity toward dopamine with detection limit as low as 20 nM.

Self-assembled multiwalled carbon nanotube films assisted by ureidopyrimidinone-based multiple hydrogen bonds.

Self-assembled functionalized multiwalled carbon nanotube (MWNT) films were successfully constructed, linked by a kind of strong binding strength from the self-complementary hydrogen-bonding array of ureidopyrimidinone-based modules (UPM) attached. Employing the feasible reaction of isocyanate containing ureidopyrimidinone with amine modified MWNTs, the UPMs composed of ureidopyrimidinone and ureido were attached to MWNTs with the content as low as 0.6 mmol/g MWNTs. Upon multiple hydrogen-bonding interactions from incorporation of the AADD (A, hydrogen-bonding acceptor; D, hydrogen-bonding donor) quadruple hydrogen bonds of ureidopyrimidinone and the double hydrogen bonds of ureido group, UPM functionalized MWNTs (MWNT-UPM) can be well dispersed in the polar solvent of N,N-dimethylformamide (DMF), while they tend to self-assemble to give a self-supported film in the apolar solvent of CHCl3. In addition, by using the multiple hydrogen-bonding interactions as the driving force, the layer-by-layer (LBL) MWNT-UPM films with high coverage on solid slides can be processed. Because of the self-association of MWNT-UPM in apolar solvent, it was found that the LBL assembly of MWNT-UPM was more favorable in the polar solvent of DMF than in the apolar solvent of CHCl3. Moreover, the hydrogen-bonding linked MWNT-UPM films showed good stability upon soaking in different solvents. Furthermore, the as-prepared LBL films showed electrochemical active behaviors, exhibiting a remarkable catalytic effect on the reduction of nifedipine.

[60]-fullerene and single-walled carbon nanotube-based ultrathin films stepwise grafted onto a self-assembled monolayer on ITO.

A step-by-step method was used to prepare homogeneous ultrathin films composed of [60]-fullerene (C60) and single-walled carbon nanotubes (SWNTs), grafted onto the functional surface of an alkylsilane self-assembled monolayer (SAM) on an ITO substrate with an ITO-C60-SWNT sequence using amine addition across a double bond in C60 followed by amidation coupling with acid-functionalized SWNTs. Atomic force microscope and scanning electron microscope images of the resulting composite film showed two-component ball-tube microstructures with high-density coverage, where C60 was homogeneously distributed in the SWNT forest. The attachment of SWNTs to the residual amine units in the SAM on the ITO substrate (SAM-ITO) as well as on the C60 sphere results in the C60 molecules in the aggregated clusters being more separately dispersed, which forms a densely packed composite film as a result of the pi-pi interaction between the C60 buckyballs and the SWNT walls. It was found using ferrocene as an internal redox probe that the oxidative and reductive processes at the film-solution surface were effectively retarded because of obstruction from the densely packed film and the electronic effect of SWNT and C60. In addition, the electrochemical properties of C60 on SAM-ITO plates observed by cyclic voltammetry were significantly modified by chemical anchorage using SWNTs. X-ray photoelectron spectroscopy (XPS) analysis also indicated the successful grafting of C60 and SWNT. The XPS chemical shift of the binding energy showed the presence of electronic interactions between C60, SWNT, and ITO components. Such a uniformly distributed C60-SWNT film may be useful for future research in electrochemical and photoactive nanodevices.