A new perspective on carbon nano-onion/nickel hydroxide/oxide composites: Physicochemical properties and application in hybrid electrochemical systems

Carbon nano-onion (CNO) and Ni(OH)₂ or NiO composites were prepared by chemical loading of Ni(OH)₂ on the carbon surface. The samples were characterized by transmission electron microscopic (TEM) and scanning electron microscopic (SEM) methods, powder X-ray diffraction (XRD) technique and by differential-thermogravimetric analyses (TGA-DTG). The porosity properties were characterized by using nitrogen gas adsorption analyses. Pristine inorganic samples of NiO and Ni(OH)₂ revealed different morphologies and porous characteristics when compared to those of the CNO composites, which showed unique electrochemical properties. The electrochemical performance of the CNO/Ni(OH)₂ or CNO/NiO composites is largely affected by the mass, the morphology, the crystal phases of the inorganic component and the distribution of the Ni(OH)₂/NiO phase. The CNO composites were used as materials for hybrid charge-storage devices.     

Detection of NO2 Down to One ppb Using Ion‐in‐Conjugation‐Inspired Polymer

Nitrogen dioxide (NO₂) emission has severe impact on human health and the ecological environment and effective monitoring of NO₂ requires the detection limit (limit of detection) of several parts‐per‐billion (ppb). All organic semiconductor‐based NO₂ sensors fail to reach such a level. In this work, using an ion‐in‐conjugation inspired‐polymer (poly(3,3′‐diaminobenzidine‐squarine, noted as PDBS) as the sensory material, NO₂ can be detected as low as 1 ppb, which is the lowest among all reported organic NO₂ sensors. In addition, the sensor has high sensitivity, good reversibility, and long‐time stability with a period longer than 120 d. Theoretical calculations reveal that PDBS offers unreacted amine and zwitterionic groups, which can offer both the H‐bonding and ion‐dipole interaction to NO₂. The moderate binding energies (≈0.6 eV) offer high sensitivity, selectivity as well as good reversibility. The results demonstrate that the ion‐in‐conjugation can be employed to greatly improve sensitivity and selectivity in organic gas sensors by inducing both H‐bonding and ion‐dipole attraction.     

Effect of calcination methods on electrochemical performance of NiO used as electrode materials for supercapacitor

Ni(OH)₂ precursors were prepared via the precipitation transformation method, which was originated from Na₂C₂O₄, NiSO₄·6H₂O and urea. NiO samples were successfully obtained by calcining Ni(OH)₂ precursor with different calcination methods. Some were calcination in a tube furnace under the nitrogen flow and others were calcination in a muffle furnace. The products were well-characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The influence of calcination methods on electrochemical performance of NiO samples were investigated. Moreover, the possible reason was proposed. The charge storage mechanism of NiO positive electrode in aqueous electrolyte was discussed. The electrochemical test showed that the as-prepared NiO prepared in a tube furnace can exhibit a good pseudocapacitance behaviour due to the higher utilization of active material.     

One-pot solvothermal synthesis of size-controlled NiO nanoparticles

In this work, NiO nanoparticles with diameter of ～4.5?nm for application as electrode material in supercapacitor were directly synthesized by an one-pot solvothermal strategy using N,N-dimethylformamide (DMF) as solvent and hexadecyl trimethyl ammonium bromide (CTAB) as additive. The experiment results indicated that CTAB is the key for the phase formation of NiO. Ni(OH)₂ phase was formed in the absence of CTAB, while NiO phase was produced in the presence of CTAB as an additive. As compared with the NiO prepared by calcination on the layer-structured Ni(OH)₂ intermediate produced in the absence of CTAB, the NiO nanoparticles prepared by this strategy had smaller particle size. Due to large specific surface area, small size and residual Ni(OH)₂, these NiO nanoparticles presented high electrochemical performance. They had high specific capacitance of 1128?F?g^?1 at low current density of 3.1?A?g^?1 and 625.0?F?g^?1 at high current density of 62.5?A?g^?1.     

Tailoring NiO Nanostructured Arrays by Sulfate Anions for Sodium‐Ion Batteries

In this contribution, a novel sulfate‐ion‐controlled synthesis is developed to fabricate freestanding nickel hydroxide nanoarrays on Ni substrate. As an inorganic morphology‐controlled agent, SO₄²⁻ ions play a critical role in controlling the crystal growth and the nanoarray morphologies, by modulating the growth rate of adsorbed crystal facets or inserting into the metal hydroxide interlayers. By controlling the SO₄²⁻ concentration, the nanostructured arrays are tailored from one‐dimensional (1D) Ni(SO₄)_0.3(OH)_1.4 nanobelt arrays to hierarchical β ‐ Ni(OH)₂ nanosheet arrays. With further graphene oxide modification and postheat treatment, the obtained NiO/graphene hybrid nanoarrays show great potential for high‐performance sodium‐ion batteries, which exhibit a cyclability of 380 mAh g⁻¹ after undergoing 100 cycles at 0.5 C and reach a rate capability of 335 mA h g⁻¹ at 10 C.     

Template Engineering of CuBi2O4 Single‐Crystal Thin Film Photocathodes

To develop strategies for efficient photo‐electrochemical water‐splitting, it is important to understand the fundamental properties of oxide photoelectrodes by synthesizing and investigating their single‐crystal thin films. However, it is challenging to synthesize high‐quality single‐crystal thin films from copper‐based oxide photoelectrodes due to the occurrence of significant defects such as copper or oxygen vacancies and grains. Here, the CuBi₂O₄ (CBO) single‐crystal thin film photocathode is achieved using a NiO template layer grown on single‐crystal SrTiO₃ (STO) (001) substrate via pulsed laser deposition. The NiO template layer plays a role as a buffer layer of large lattice mismatch between CBO and STO (001) substrate through domain‐matching epitaxy, and forms a type‐II band alignment with CBO, which prohibits the transfer of photogenerated electrons toward bottom electrode. The photocurrent densities of the CBO single‐crystal thin film photocathode demonstrate ?0.4 and ?0.7 mA cm^?2 at even 0 V_RHE with no severe dark current under illumination in a 0.1 m potassium phosphate buffer solution without and with H₂O₂ as an electron scavenger, respectively. The successful synthesis of high‐quality CBO single‐crystal thin film would be a cornerstone for the in‐depth understanding of the fundamental properties of CBO toward efficient photo‐electrochemical water‐splitting.     

Kinetics-Driven Dual Hydrogen Spillover Effects for Ultrasensitive Hydrogen Sensing

Palladium (Pd)-modified metal oxide semiconductors (MOSs) gas sensors often exhibit unexpected hydrogen (H₂) sensing activity through a spillover effect. However, sluggish kinetics over a limited Pd-MOS surface seriously restrict the sensing process. Here, a hollow Pd-NiO/SnO₂ buffered nanocavity is engineered to kinetically drive the H₂ spillover over dual yolk-shell surface for the ultrasensitive H₂ sensing. This unique nanocavity is found and can induce more H₂ absorption and markedly improve kinetical H₂ ab/desorption rates. Meanwhile, the limited buffer-room allows the H₂ molecules to adequately spillover in the inside-layer surface and thus realize dual H₂ spillover effect. Ex situ XPS, in situ Raman, and density functional theory (DFT) analysis further confirm that the Pd species can effectively combine H₂ to form Pd-H bonds and then dissociate the hydrogen species to NiO/SnO₂ surface. The final Pd-NiO/SnO₂ sensors exhibit an ultrasensitive response (0.1–1000 ppm H₂) and low actual detection limit (100 ppb) at the operating temperature of 230 °C, which surpass that of most reported H₂ sensors.     

Non-basic solution eco-routes to nano-scale NiO with different shapes: Synthesis and application

The assembly of NiO nanodiscs (namely nanoflowers) as well as the dispersed NiO nanodiscs have been successfully synthesized via the thermal decomposition of Ni(OH)₂ obtained from different Ni sources in non-basic solution. The route is environment-friendly. The materials were characterized by X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM) and N₂ adsorption–desorption. The porous structures with pore size around 6 nm can be observed on the single NiO disc. The nanoflowers exhibit better performance than nanodiscs in the electrochemical test and water treatment experiments, due to much more available surface areas and spaces formed in the NiO nanoflowers.     

Surface Oxidation of AuNi Heterodimers to Achieve High Activities toward Hydrogen/Oxygen Evolution and Oxygen Reduction Reactions

Although much attention has been paid to the exploration of highly active electrocatalysts, especially catalysts for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), the development of multifunctional catalysts remains a challenge. Here, we utilize AuNi heterodimers as the starting materials to achieve high activities toward HER, OER and ORR. The HER and ORR activities in an alkali environment are similar to those of Pt catalysts, and the OER activity is very high and better than that of commercial IrO₂. Both the experimental and calculated results suggest that the surface oxidation under oxidative conditions is the main reason for the different activities. The NiO/Ni interface which exists in the as‐synthesized heterodimers contributes to high HER activity, the Ni(OH)₂‐Ni‐Au interface and the surface Ni(OH)₂ obtained in electrochemical conditons gives rise to promising ORR and OER activities, respectively. As a comparison, a Au@Ni core‐shell structure is also synthesized and examined. The core‐shell structure shows lower activities for HER and OER than the heterodimers, and reduces O₂ selectively to H₂O₂. The work here allows for the development of a method to design multifunctional catalysts via the partial oxidation of a metal surface to create different active centers.     

A facile preparation of graphene/reduced graphene oxide/Ni(OH)2 two dimension nanocomposites for high performance supercapacitors

A Ni(OH)₂ composite with good electrochemical performances was prepared by a facile method. Ni(OH)₂ was homogeneously grown on the hydrophilic graphene/graphene oxide (G/GO) nanosheets, which can be prepared in large scale in my lab. Then G/GO/Ni(OH)₂ was reduced by L-Ascorbic acid to obtain G/RGO/Ni(OH)₂. Caused by the synergy effects among the components, the G/RGO/Ni(OH)₂ electrode showed good electrochemical properties. The G/RGO/Ni(OH)₂ electrode possessed a specific capacitance as high as 1510 F g⁻¹ at 2 A g⁻¹ and even 890 F g⁻¹ at 40 A g⁻¹. An asymmetric supercapacitor device consisting of G/RGO/Ni(OH)₂ and reduced graphene oxide (RGO) was installed and displayed a high energy density of 44.9 W h kg⁻¹ at the power energy density of 400.1 W kg⁻¹. It was verified that the G/GO nanosheets are ideal supporting material in supercapacitor.     

Highly Concentrated,Ultrathin Nickel Hydroxide Nanosheet Ink for Wearable Energy Storage Devices

Solution‐based techniques are considered as a promising strategy for scalable fabrication of flexible electronics owing to their low‐cost and high processing speed. The key to the success of these techniques is dominated by the ink formulation of active nanomaterials. This work successfully prepares a highly concentrated two dimensional (2D) crystal ink comprised of ultrathin nickel hydroxide (Ni(OH)₂) nanosheets with an average lateral size of 34 nm. The maximum concentration of Ni(OH)₂ nanosheets in water without adding any additives reaches as high as 50 mg mL^?1, which can be printed on arbitrary substrates to form Ni(OH)₂ thin films. As a proof‐of‐concept application, Ni(OH)₂ nanosheet ink is coated on commercialized carbon fiber yarns to fabricate wearable energy storage devices. The thus‐fabricated hybrid supercapacitors exhibit excellent flexibility with a capacitance retention of 96% after 5000 bending–unbending cycles, and good weavability with a high volumetric capacitance of 36.3 F cm^?3 at a current density of 0.4 A cm^?3, and an energy density of 11.3 mWh cm^?3 at a power density of 0.3 W cm^?3. As a demonstration of practical application, a red light emitting diode can be lighted up by three hybrid devices connected in series.     

Effects of single electrodes of Ni(OH)2 and activated carbon on electrochemical performance of Ni(OH)2–activated carbon asymmetric supercapacitor

Nickel hydroxide consisting of loosely packed nanospheres was synthesized as positive electrode material for an asymmetric capacitor based on Ni(OH)₂ and activated carbon (AC). Two series of supercapacitors were fabricated to investigate the effects of the single electrodes of Ni(OH)₂ and AC on the electrochemical performance of asymmetric Ni(OH)₂–AC capacitor. Parameters including cell voltage window, specific capacitance and cyclic stability were assessed. In one series of supercapacitors, mass of Ni(OH)₂ was excessive while mass of AC was varied, the AC electrode thus constrained both the capacitance and the upper limit of cell voltage. Deficiency of AC resulted in lower specific capacitance and narrower cell voltage window but benefited to cyclic stability. In the other series of supercapacitors, the mass of AC was excessive whereas the mass of Ni(OH)₂ was changeable in each cell, Ni(OH)₂ electrode thus dominated both the capacitance and the lower limit of cell voltage. As a consequence, deficiency of Ni(OH)₂ led to higher specific capacity and wider cell voltage window as well as lower cyclic stability. These results can contribute to improving understanding of and optimizing performance of asymmetric Ni(OH)₂–AC capacitor.     

Rational Design of Nanoporous MoS2/VS2 Heteroarchitecture for Ultrahigh Performance Ammonia Sensors

2D transition metal dichalcogenides (TMDs) have received widespread interest by virtue of their excellent electrical, optical, and electrochemical characteristics. Recent studies on TMDs have revealed their versatile utilization as electrocatalysts, supercapacitors, battery materials, and sensors, etc. In this study, MoS₂ nanosheets are successfully assembled on the porous VS₂ (P‐VS₂) scaffold to form a MoS₂/VS₂ heterostructure. Their gas‐sensing features, such as sensitivity and selectivity, are investigated by using a quartz crystal microbalance (QCM) technique. The QCM results and density functional theory (DFT) calculations reveal the impressive affinity of the MoS₂/VS₂ heterostructure sensor toward ammonia with a higher adsorption uptake than the pristine MoS₂ or P‐VS₂ sensor. Furthermore, the adsorption kinetics of the MoS₂/VS₂ heterostructure sensor toward ammonia follow the pseudo‐first‐order kinetics model. The excellent sensing features of the MoS₂/VS₂ heterostructure render it attractive for high‐performance ammonia sensors in diverse applications.     

A High‐Energy‐Density Hybrid Supercapacitor with P‐Ni(OH)2@Co(OH)2 Core–Shell Heterostructure and Fe2O3 Nanoneedle Arrays as Advanced Integrated Electrodes

Transition metal hydro/oxides (TMH/Os) are treated as the most promising alternative supercapacitor electrodes thanks to their high theoretical capacitance due to the various oxidation states and abundant cheap resources of TMH/Os. However, the poor conductivity and logy reaction kinetics of TMH/Os severely restrict their practical application. Herein, hierarchical core–shell P‐Ni(OH)₂@Co(OH)₂ micro/nanostructures are in situ grown on conductive Ni foam (P‐Ni(OH)₂@Co(OH)₂/NF) through a facile stepwise hydrothermal process. The unique heterostructure composed of P‐Ni(OH)₂ rods and Co(OH)₂ nanoflakes boost the charge transportation and provide abundant active sites when used as the intergrated cathode for supercapacitors. It delivers an ultrahigh areal specific capacitance of 4.4 C cm^?2 at 1 mA cm^?2 and the capacitance can maintain 91% after 10 000 cycles, showing an ultralong cycle life. Additionally, a hybrid supercapacitor composed with P‐Ni(OH)₂@Co(OH)₂/NF cathode and Fe₂O₃/CC anode shows a wider voltage window of 1.6 V, a remarkable energy density of 0.21 mWh cm^?2 at the power density of 0.8 mW cm^?2, and outstanding cycling stability with about 81% capacitance retention after 5000 cycles. This innovative study not only supplies a newfashioned electronic apparatus with high‐energy density and cycling stability but offers a fresh reference and enlightenment for synthesizing advanced integrated electrodes for high‐performance hybrid supercapacitors.     

Synthesis of NiO nanowalls by thermal treatment of Ni film deposited onto a stainless steel substrate

Two-dimensional nanostructures have a variety of applications due to their large surface areas. In this study, the authors present a simple and convenient method to realize two-dimensional NiO nanowalls by thermal treatment of a Ni thin film deposited by sputtering onto a stainless steel substrate. The substrate surface area is supposed to be significantly increased by creating nanowalls. The effects on the nanowall morphology of the thermal treatment temperature and duration are investigated. A mechanism based on the surface diffusion of Ni(2+) ions from the Ni?base film is then proposed for the growth of the NiO nanowalls. The as-synthesized NiO nanowalls are characterized by scanning electron microscopy, energy-dispersive x-ray analysis, x-ray diffraction, transmission electron microscopy and high resolution transmission electron microscopy.     

UV–Ozone Interfacial Modification in Organic Transistors for High‐Sensitivity NO2 Detection

A new type of nitrogen dioxide (NO₂) gas sensor based on copper phthalocyanine (CuPc) thin film transistors (TFTs) with a simple, low‐cost UV–ozone (UVO)‐treated polymeric gate dielectric is reported here. The NO₂ sensitivity of these TFTs with the dielectric surface UVO treatment is ≈400× greater for [NO₂] = 30 ppm than for those without UVO treatment. Importantly, the sensitivity is ≈50× greater for [NO₂] = 1 ppm with the UVO‐treated TFTs, and a limit of detection of ≈400 ppb is achieved with this sensing platform. The morphology, microstructure, and chemical composition of the gate dielectric and CuPc films are analyzed by atomic force microscopy, grazing incident X‐ray diffraction, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, revealing that the enhanced sensing performance originates from UVO‐derived hydroxylated species on the dielectric surface and not from chemical reactions between NO₂ and the dielectric/semiconductor components. This work demonstrates that dielectric/semiconductor interface engineering is essential for readily manufacturable high‐performance TFT‐based gas sensors.     

Exposing {001} Crystal Plane on Hexagonal Ni‐MOF with Surface‐Grown Cross‐Linked Mesh‐Structures for Electrochemical Energy Storage

Hexagonal nickel‐organic framework (Ni‐MOF) [Ni(NO₃)₂·6H₂O, 1,3,5‐benzenetricarboxylic acid, 4‐4′‐bipyridine] is fabricated through a one‐step solvothermal method. The {001} crystal plane is exposed to the largest hexagonal surface, which is an ideal structure for electron transport and ion diffusion. Compared with the surrounding rectangular crystal surface, the ion diffusion length through the {001} crystal plane is the shortest. In addition, the cross‐linked porous mesh structures growing on the {001} crystal plane strengthen the mixing with conductive carbon, inducing preferable conductivity, as well as increasing the area of ion contact and the number of active sites. These advantages enable the hexagonal Ni‐MOF to exhibit excellent electrochemical performance as supercapacitor electrode materials. In a three‐electrode cell, specific capacitance of hexagonal Ni‐MOF in the 3.0 m KOH electrolyte is 977.04 F g^?1 and remains at the initial value of 92.34% after 5,000 cycles. When the hexagonal Ni‐MOF and activated carbon are assembled into aqueous devices, the electrochemical performance remains effective.     

Bias-independent growth of carbon nanowalls by microwave electron-cyclotron resonance plasma CVD

The investigations reported here describe the synthesis of carbon nanowalls (CNWs) by microwave electron-cyclotron resonance (ECR) plasma-assisted chemical vapour deposition (PACVD) process without an application of external bias to the substrate during growth. CNWs were grown on silicon (Si) substrates using hydrogen (H₂)/methane (CH₄) plasma at 650°C substrate temperature. Nickel (Ni) was used as a catalyst for the synthesis of CNWs. To the best of our knowledge, this is the first report that describes the bias-independent growth of CNWs using the ECR PACVD process. Formation of CNWs is confirmed by scanning electron microscopy and Raman spectroscopy. The discussion part also includes a possible growth mechanism for CNWs in terms of the role of surface plasmons.     

Fabrication of hollow mesoporous NiO hexagonal microspheres via hydrothermal process in ionic liquid

The novel NiO hexagonal hollow microspheres have been successfully prepared by annealing Ni(OH)₂, which was synthesized via an ionic liquid-assisted hydrothermal method. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption and Fourier transform infrared spectrometer (FTIR). The results show that the hollow NiO microstructures are self-organized by mesoporous cubic and hexagonal nanocrystals. The mesoporous structure possessed good thermal stability and high specific surface area (ca. 83 m²/g). The ionic liquid 1-butyl-3methylimidazolium tetrafluoroborate ([Bmim][BF₄]) was found to play a key role in controlling the morphology of NiO microstructures during the hydrothermal process. The special hollow mesoporous architectures will have potential applications in many fields, such as catalysts, absorbents, sensors, drug-delivery carriers, acoustic insulators and supercapacitors.     

α‐Ni(OH)2 Originated from Electro‐Oxidation of NiSe2 Supported by Carbon Nanoarray on Carbon Cloth for Efficient Water Oxidation

Development of effective oxygen evolution reaction (OER) electrocatalysts has been intensively studied to improve water splitting efficiency and cost effectiveness in the last ten years. However, it is a big challenge to obtain highly efficient and durable OER electrocatalysts with overpotentials below 200 mV at 10 mA cm^?2 despite the efforts made to date. In this work, the successful synthesis of supersmall α‐Ni(OH)₂ is reported through electro‐oxidation of NiSe₂ loaded onto carbon nanoarrays. The obtained α‐Ni(OH)₂ shows excellent activity and long‐term stability for OER, with an overpotential of only 190 mV at the current density of 10 mA cm^?2, which represents a highly efficient OER electrocatalyst. The excellent activity could be ascribed to the large electrochemical surface area provided by the carbon nanoarray, as well as the supersmall size (≈10 nm) of α‐Ni(OH)₂ which possess a large number of active sites for the reaction. In addition, the phase evolution of α‐Ni(OH)₂ from NiSe₂ during the electro‐oxidation process was monitored with in situ X‐ray absorption fine structure (XAFS) analysis.