Amorphous Nickel Boride Research Articles

In situ decoration of 0D-nickel boride on 2D-vanadium MXene composites: An advanced electrode material for high energy density supercapacitors

Vanadium carbide-MXene (V2CTx) is considered a rising star among 2D materials and is an ideal electrode material for energy storage due to its unique features. However, oxidation and layer restacking can impair specific capacity (Cs) and cycling performance. Considering this challenge, we have developed a composite material consisting of amorphous nickel boride (NixB NPs) and V2CTx. To prevent oxidation and restacking of the layers and to improve the performance of the supercapacitor, NixB was decorated between the gaps and the surface. The V2CTx and its composites were prepared by simple etching and direct liquid-phase methods. Under the optimized conditions, the NixB/V2CTx modified nickel foam exhibited an improved Cs value of 705.9 C g−1 and a rate capability of 53.8 % at a current density of 10 A g−1; the excellent cycling stability was 120.5 % after 10,000 cycles at 10 A g−1 in 3 M KOH. The improved Cs values, shortened ion diffusion paths, swift electron transfer, and excellent cycling stability of the composites are due to the V2CTx layers surface entrapped/gaps filled by the NixB NPs. For practical application, an asymmetric device with NixB/V2CTx and reduced graphene oxide (rGO) as positive and negative electrodes was fabricated. The NixB/V2CTx//rGO device achieved a maximum energy density of 50.22 Wh kg−1 at 800 W kg−1 and 26 Wh kg−1 at 16000 W kg−1. The capacity retention was 89.98 % and the Coulombic efficiency was 99.9 % after 20,000 continuous cycles at 8 A g−1. These results emphasized that the developed 0D/2D NixB/V2CTx electrode materials with novel composite architecture are suitable for advanced energy storage applications.

Fabrication of 0D/2D amorphous NixB/ZnIn2S4 S-scheme for enhanced photocatalytic hydrogen evolution performance

The design and synthesis of low-cost hydrogen evolution photocatalysts with high carrier separation capability and visible light responsiveness are key factors in increasing hydrogen production. In this work, zero-dimensional (0D) amorphous nickel boride (NixB) was synthesized using a reduction method. Subsequently, a 0D/2D amorphous NixB/ZnIn2S4 S-scheme heterojunction was fabricated through electrostatic attraction. This heterojunction exhibited stronger visible light responsiveness and enhanced photogenerated carrier separation performance. The morphology, composition, elemental, structural, and light absorption capacities of the as-synthesized composites were researched by SEM, TEM, XRD, XPS, and UV–vis DRS. The ability to separate photogenerated carriers were evaluated through photoelectrochemical experiments. The hydrogen evolution rate of NixB/ZnIn2S4 (2208 μmol h−1 g−1) increased 25 times than that of single ZnIn2S4 in sacrificial solution, and the apparent quantum yield (AQY) at 400 nm was 14.25 %. This study gives evidence of the great preponderance of S-scheme heterojunction and multidimensional material co-construction in improving hydrogen precipitation.

Insight into the synergistic effect of 2D/2D layered metal selenides wrapped nickel boride nanoparticles based ternary heterostructure for constructing asymmetric supercapacitors with excellent energy density

Tuning the structural and electronic properties of layered metal selenides is a highly feasible approach for developing high-performance asymmetric supercapacitors (ASCs). In this work, a ternary heterostructure of yttrium diselenide/molybdenum diselenide (YSe2/MoSe2) with amorphous nickel boride nanoparticles (NixB NPs) was prepared by a simple hydrothermal method followed by a liquid phase route. Interestingly, this ternary heterostructure consists of multiple layers of YSe2/MoSe2 nanosheets uniformly wrapped by NixB NPs over the entire surface. The characterization results by X-ray diffraction, Raman, and X-ray photoelectron spectroscopy showed that the strong synergism between YSe2/MoSe2 and NixB NPs indicates an obvious electron transfer from NixB to the YSe2/MoSe2 hybrid, which contributes to the enhancement of the electrical conductivity of the electrode. Due to its exclusive heterostructure network, the single YSe2/MoSe2/NixB electrode achieved a specific capacitance of 893.3 F/g at 1 A/g and a capacity retention of 128.17% over 5000 cycles. In addition, the asymmetric YSe2/MoSe2/NixB||rGO device with a working potential of 1.6 V showed an impressive energy density of 39.5 Wh kg−1 with a power density of 800 W kg−1 and excellent cycling stability with 85.60% capacity retention after 5000 cycles in aqueous electrolyte. This result of the designed ASC device encourages the development of a new platform for the design of electrode materials based on metal selenides and metal borides.

Amorphous iron-doped nickel boride with facilitated structural reconstruction and dual active sites for efficient urea electrooxidation

Designing transition metal-based catalysts for efficient urea oxidation reaction (UOR) is important for realizing energy-saving hydrogen production via urea-rich (waste)water electrolysis. Herein, we have developed an iron-doped amorphous nickel boride electrocatalyst (aFe-NiB) for UOR. Compared with the undoped and crystalline counterparts, aFe-NiB exhibits a higher activity and the benchmark current density of 10 mA cm−2 can be attained at 1.298 V vs. reversible hydrogen electrode (RHE). Coupled with an efficient hydrogen evolution catalyst, the aFe-NiB-assisted urine electrolyzer can attain a 46 times higher H2 production rate than the water electrolyzer at 1.50 V. Further study reveals a crystallinity-dependent structure self-reconstruction process during UOR. aFe-NiB attains complete phase evolution from boride to electroactive Fe-doped NiOOH. In addition, density functional theory calculations imply that Fe dopants can improve intrinsic catalytic activity via electronic structure regulation of the self-evolved NiOOH and forming heterogeneous bimetallic active sites for UOR. This study provides meaningful insights into the crystallinity-dependent UOR performance and effective strategies to develop efficient UOR (pre)catalysts with dual active sites. Significantly, the demonstrated direct wastewater (urine) electrolysis paves the way for net zero buildings -targeted human waste reutilization.

Development of an Amorphous Nickel Boride/Manganese Molybdate Heterostructure as an Efficient Electrode Material for a High-Performance Asymmetric Supercapacitor.

The exploration of heterostructure materials with unique electronic properties is considered a desirable platform for fabricating electrode/surface interface relationships for constructing asymmetric supercapacitors (ASCs) with high energy density. In this work, a heterostructure based on amorphous nickel boride (NiXB) and crystalline square bar-like manganese molybdate (MnMoO4) was prepared by a simple synthesis strategy. The formation of the NiXB/MnMoO4 hybrid was confirmed by powder X-ray diffraction (p-XRD), field emission scanning electron microscopy (FE-SEM), field-emission transmission electron microscopy (FE-TEM), Brunauer-Emmett-Teller (BET), Raman, and X-ray photoelectron spectroscopy (XPS). In this hybrid system (NiXB/MnMoO4), the intact combination of NiXB and MnMoO4 leads to a large surface area with open porous channels and abundant crystalline/amorphous interfaces with a tunable electronic structure. This NiXB/MnMoO4 hybrid shows high specific capacitance (587.4 F g-1) at 1 A g-1, and it even retains a capacitance of 442.2 F g-1 at 10 A g-1, indicating superior electrochemical performance. The fabricated NiXB/MnMoO4 hybrid electrode also exhibited an excellent capacity retention of 124.4% (10000 cycles) and a Coulombic efficiency of 99.8% at a current density of 10 A g-1. In addition, the ASC device (NiXB/MnMoO4//activated carbon) achieved a specific capacitance of 104 F g-1 at 1 A g-1 and delivered a high energy density of 32.5 Wh.kg-1 with a power density of 750 W·kg-1. This exceptional electrochemical behavior is due to the ordered porous architecture and the strong synergistic effect of NiXB and MnMoO4, which enhances the accessibility and adsorption of OH- ions that improve electron transport. Moreover, the NiXB/MnMoO4//AC device exhibits excellent cyclic stability with a retention of 83.4% of the original capacitance after 10000 cycles, which is due to the heterojunction layer between NiXB and MnMoO4 that can improve the surface wettability without causing structural changes. Our results show that the metal boride/molybdate-based heterostructure is a new category of high-performance and promising material for the growth of advanced energy storage devices.

Heterostructure of amorphous nickel boride anchored 2D-layered cobalt selenide nanosheets as a disposable strip sensor for detection of toxic pollutant 5-nitroquinoline in aquatic samples

The development of disposable electrode-based sensors is of great importance for the electrochemical monitoring of toxic pollutants in wastewater systems, which are often present and mutually inhibiting during sample detection. In this work, a distinctive approach was taken to use an electrochemical heterostructure sensor with chemically reduced nickel boride (Ni3B) nanoparticles anchored in two-dimensional (2D) layered cobalt selenide (CoSe) nanosheets. The prepared hybrid structure (2D CoSe/Ni3B) enables large active sites and a strong synergistic effect between nanostructures to improve the electrocatalytic activity in the detection of water pollutant 5-nitroquinoline (5-NQ) with a disposable screen-printed carbon electrode (SPCE). The 2D CoSe/Ni3B/SPCE exhibits a reduction peak potential of −0.63 V for 5-NQ, with an increased reduction peak current compared to that of other electrodes. The fabricated disposable strip electrode is suitable for the electrochemical testing of pollutants. The proposed hybrid 2D CoSe/Ni3B/SPCE disposable sensor showed a wide linear range of 0.2–378 μM and a low detection limit of 0.042 μM for 5-NQ. The developed 2D CoSe/Ni3B hybrid nanostructure-based disposable sensor efficiently detects 5-NQ in hazardous water contaminants by voltammetric analysis and showed acceptable recoveries. Based on the results, it is believed that the proposed work provides a clear idea for the fabrication of transition metal-based metal boride and selenide heterostructures with excellent catalytic activity for the electrochemical detection of various pollutants in real-time monitoring.

Composition Engineering of Amorphous Nickel Boride Nanoarchitectures Enabling Highly Efficient Electrosynthesis of Hydrogen Peroxide.

Developing advanced electrocatalysts with exceptional two electron (2e- ) selectivity, activity, and stability is crucial for driving the oxygen reduction reaction (ORR) to produce hydrogen peroxide (H2 O2 ). Herein, a composition engineering strategy is proposed to flexibly regulate the intrinsic activity of amorphous nickel boride nanoarchitectures for efficient 2e- ORR by oriented reduction of Ni2+ with different amounts of BH4 - . Among borides, the amorphous NiB2 delivers the 2e- selectivity close to 99% at 0.4V and over 93% in a wide potential range, together with a negligible activity decay under prolonged time. Notably, an ultrahigh H2 O2 production rate of 4.753mol gcat -1 h-1 is achieved upon assembling NiB2 in the practical gas diffusion electrode. The combination of X-ray absorption and in situ Raman spectroscopy, as well as transient photovoltage measurements with density functional theory, unequivocally reveal that the atomic ratio between Ni and B induces the local electronic structure diversity, allowing optimization of the adsorption energy of Ni toward *OOH and reducing of the interfacial charge-transfer kinetics to preserve the OO bond.

Ultrathin Two-Dimensional ZnIn2S4/Nix-B Heterostructure for High-Performance Photocatalytic Fine Chemical Synthesis and H2 Generation.

Photocatalytic H2 evolution coupled with organic transformation provides a new avenue to cooperatively produce clean fuels and fine chemicals, enabling a more efficient conversion of solar energy. Here, a novel two-dimensional (2D) heterostructure of ultrathin ZnIn2S4 nanosheets decorated with amorphous nickel boride (Nix-B) is prepared for simultaneous photocatalytic anaerobic H2 generation and aromatic aldehydes production. This ZnIn2S4/Nix-B catalyst elaborately combines the ultrathin structure advantage of the ZnIn2S4 semiconductor and the cocatalytic function of Nix-B. A high H2 production rate of 8.9 mmol h-1 g-1 is delivered over the optimal ZnIn2S4/Nix-B with a stoichiometric production of benzaldehyde, which is about 22 times higher than ZnIn2S4. Especially, the H2 evolution rate is much higher than the value (2.8 mmol h-1 g-1) of the traditional photocatalytic half reaction of H2 production with triethanolamine as a sacrificial agent. The apparent quantum yield reaches 24% at 420 nm, representing an advanced photocatalyst system. Moreover, compared with traditional sulfide, hydroxide, and even noble metal modified ZnIn2S4/M counterparts (M = NiS, Ni(OH)2, Pt), the ZnIn2S4/Nix-B also maintains markedly higher photocatalytic activity, showing a highly efficient and economical advantage of the Nix-B cocatalyst. This work sheds light on the exploration of 2D ultrathin semiconductors decorated with novel transition metal boride cocatalyst for efficient photocatalytic organic transformation integrated with solar fuel production.

Cobalt nickel boride nanocomposite as high-performance anode catalyst for direct borohydride fuel cell

Similar to MXene, MAB is a group of 2D ceramic/metallic boride materials which exhibits unique properties for various applications. However, these 2D sheets tend to stack and therefore lose their active surface area and functions. Herein, an amorphous cobalt nickel boride (Co–Ni–B) nanocomposite is prepared with a combination of 2D sheets and nanoparticles in the center to avoid agglomeration. This unique structure holds the 2D nano-sheets with massive surface area which contains numerous catalytic active sites. This nanocomposite is prepared as an electrocatalyst for borohydride electrooxidation reaction (BOR). It shows outstanding catalytic activity through improving the kinetic parameters of BH4− oxidation, owing to abundant ultrathin 2D structure on the surface, which provide free interspace and electroactive sites for charge/mass transport. The anode catalyst led to a 209 mW/cm2 maximum power density with high open circuit potential of 1.06 V at room temperature in a miniature direct borohydride fuel cell (DBFC). It also showed a great longevity of up to 45 h at an output power density of 64 mW/cm2, which is higher than the Co–B, Ni–B and PtRu/C. The cost reduction and prospective scale-up production of the Co–Ni–B catalyst are also addressed.

Promoting the Na+-storage of NiCo2S4 hollow nanospheres by surfacing Ni–B nanoflakes

Sodium ion battery (SIB) is considered as the potential alternative for next generation energy system to succeed the lithium ion battery (LIB) due to the low price and vast abundance of Na resource. Ternary metal sulfide is identified as an important redox conversion type of negative electrode for SIB. In this study, amorphous nickel boride (Ni-B) nanoflakes are introduced into the hollow Ni-Co sulfide nanospheres by a facile in situ solution growth route to promote the electrochemical performance of Na+-storage. Electrochemical measurements demonstrate that the Ni-B component could effectively improve the redox kinetics of the conversion reaction and structural stability during long-term Na+ insertion/extraction. For example, the NiCo2S4@Ni–B composites display a high reversible capacity of 251.9 mA h g−1 at the current density of 1.0 A g−1 after 200 cycles, much higher than that of bare NiCo2S4 (37.4 mA h g−1 at 1.0 A g−1 after 200 cycles). As a consequence, these results demonstrate a new sight to explore heterostructures of mixed metal-sulfides electrode materials with superior Na+-storage performances.

Metal–organic framework (MOF)-derived amorphous nickel boride: an electroactive material for electrochemical energy conversion and storage application

A single step redox approach that transformed the crystalline Ni-MOF to amorphous nickel boride (NiB) nanostructures showed excellent electrocatalytic (oxygen evolution reaction; OER) and charge storage (supercapacitor) performances.

Electroless Plating of Transition Metal Boride with High Boron Content as Superior HER Electrocatalyst

AbstractFacile deposition of transition metal boride (TMB) with high‐boron content as highly efficient hydrogen evolution reaction (HER) electrocatalyst has been realized by a facile one‐step electroless‐plating (EP) method. Boron content of the TMB catalyst shows an appreciable impact on its intrinsic HER activity. NiB/NF electrode with thin amorphous nickel boride (NiB) deposition on nickel foam (NF) required overpotential of only 41.2 mV to deliver a current density of 10 mA cm−2 for HER in 1.0 M KOH alkaline electrolyte. Meanwhile, this kind of electrode also shows satisfied stability which can work at large current density of 1000 mA cm−2 for over 72 h without performance degradation. The advance on the TMB electrode may pave a way to the development of practical electrodes for water splitting.

Crystalline nickel boride nanoparticle agglomerates for enhanced electrocatalytic methanol oxidation

In this paper, crystalline Ni3B nanoparticle agglomerates have been successfully prepared via dry-powder annealing of the solution-produced amorphous nickel boride. The electron microscopy (EM) images indicate that the Ni3B nanomaterial is composed of numerous nano-sized particles with a diameter ranging from 100 to 200 nm. The electrocatalytic characteristics of nickel boride in an alkaline medium were observed by cyclic voltammetry (CV) and chronoamperomerty (CA). Compared to the amorphous nickel boride/Ni foam (ANB/NF), the crystalline Ni3B/Ni foam (CNB/NF) electrode exhibits a higher catalytic performance with low initial oxidation potential of 0.35 V and a high anodic oxidation current density of 62 A g−1 at 0.55 V in a 6 M KOH solution with 0.5 M methanol. And the CNB/NF electrode shows good long-term cycling stability and the catalytic current of methanol retains 87% of the initial value after 1000 time cycles. The CNB/NF electrode should be a promising candidate for alkaline direct methanol fuel cells (DMFCs).

Amorphous nickel boride membrane coated PdCuCo dendrites as high-efficiency catalyst for oxygen reduction and methanol oxidation reaction

Extensive efforts have been devoted to improve electrocatalytic activity of the catalysts in the fuel cells, however, it's still a big challenge to obtain the catalysts with low-cost and high-efficiency. Here we report the branched PdCuCo catalyst coated by amorphous nickel boride membrane displays an effective activity toward oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The coating membrane serves as an electron acceptor to tune the surface electronic structure of the catalyst. And the interactional effect of the composite catalysts exhibit a normal distribution trend of mass activity (MA) and specific activity (SA) for the ORR and MOR. The SA of the composite catalysts effectively improves 3.3 times for ORR and 4.1 times for MOR than PdCuCo. Moreover, the proposed cost-effective catalyst can inspire novel design perspective about the focus attention of catalytic activity.

Communication—Facile Synthesis of Amorphous Nickel Boride Nanoparticles for Highly Sensitive Non-Enzyme Glucose Detection

Amorphous nickel boride (NB) nanoparticles are facilely synthesized by one-step chemical precipitation and for the first time applied for glucose oxidation. Benefiting from the merits of uniform nano-morphology and highly-dispersed Ni, the achieved NB-modified electrode exhibits excellent electrochemical performances with high sensitivity for non-enzyme glucose detection.

Facile Synthesis of Amorphous Ternary Metal Borides-Reduced Graphene Oxide Hybrid with Superior Oxygen Evolution Activity.

Metal borides represent an emerging family of advanced electrocatalyst for oxygen evolution reaction (OER). Herein, we present a fast and simple method of synthesizing iron-doped amorphous nickel boride on reduced graphene oxide (rGO) sheets. The hybrid exhibits outstanding OER performance and stability in prolonged OER operation. In 1.0 M KOH, only 230 mV is required to afford a current density of 15 mA cm-2 with a small Tafel slope of 50 mV dec-1. DFT calculations lead to a suggestion that the in situ formation of MO xH y during electrochemical activation acts as active sites for water oxidation. The superior OER activity of the as-prepared catalyst is attributed to (i) its unique amorphous structure to allow abundant active sites, (ii) synergistic effect of constituents, and (iii) strong coupling of active material and highly conductive rGO. This work not only provides new perspectives to design a highly effective material for OER but also opens a promising avenue to tailor the electrochemical properties of metal borides, which could be extended to other materials for energy storage and conversion technologies.

Nickel Boride Cocatalyst Boosting Efficient Photocatalytic Hydrogen Evolution Reaction

Noble metals have been extensively used as catalyst promoters to driven highly efficient photocatalytic hydrogen evolution reaction (HER). However, noble-metal-based promoters are limited by their expensive costs and scarcities. Recently, massive efforts have been focused on metal phosphides, metal sulfides, and metal carbides as cocatalysts to achieve high HER performance. Currently, metal borides were reported as promoters for hydrogen evolution. Here, we demonstrate amorphous nickel boride (NiB) with a suitable band gap prepared by the chemical reduction of nickel nitrate hexahydrate using sodium borohydride as a cocatalyst over graphite carbon nitride (C3N4), thus achieving higher hydrogen evolution performance than C3N4. With the B(δ−)–Ni(δ+)–N(δ−) bonds between NiB and C3N4, the as-prepared C3N4/NiB7.5 shows a dramatically enhanced photocatalytic hydrogen generation rate (464.4 μmol h–1 g–1), and reaches a quantum efficiency of 10.92% with 365 nm light irradiation.

Enhancement of photoelectrochemical oxidation by an amorphous nickel boride catalyst on porous BiVO4.

This paper describes an amorphous nickel boride (NiB) electrocatalyst loaded on porous bismuth vanadate (BiVO4) with high activity for oxygen evolution in photoelectrochemical water oxidation. The NiB-decorated BiVO4 photoanode exhibits an onset potential of 0.25 V versus the reversible hydrogen electrode (vs. RHE) and a photocurrent of 3.47 mA cm-2 at 1.23 V vs. RHE under simulated 100 mW cm-2 irradiation.

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum–nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum–nickel catalyst, and this composite catalyst composed of crystalline platinum–nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Nanostructured Amorphous Nickel Boride for High‐Efficiency Electrocatalytic Hydrogen Evolution over a Broad pH Range

AbstractA fruitful paradigm in the development of low‐cost and efficient water splitting systems for hydrogen generation is to search the highly active non‐noble catalysts towards hydrogen evolution reaction (HER). Here, the electrocatalytic HER activity of nanostructured amorphous nickel boride (Ni−B) alloy has been investigated. Amorphous Ni−B has exhibited excellent catalytic efficiency and long‐term stability for HER over a broad pH range, which is actually comparable to the performance of Pt. This high catalytic activity is due to the amorphous structure and the moderate electron structure of Ni−B. The Ni−B catalyst is easily obtained via electroless plating technique and we could get a supported Ni−B catalyst on desired substrates. Given the low cost, abundance, corrosion resistance, high efficiency and ease of fabrication, amorphous Ni−B is among the best alternatives to noble metal hydrogen evolution catalysts for water splitting.