Nickel Species Research Articles

A Photoinduced, Nickel‐Catalyzed Reaction for the Stereoselective Assembly of C‐Linked Glycosides and Glycopeptides

AbstractC‐Alkyl glycosides and glycoproteins exist in natural products and are prized for their role as carbohydrate mimics in drug design. However, a practical strategy that merges glycosyl donors with readily accessible reagents, derived from abundant carboxylic acid and amine feedstocks, is yet to be conceived. Herein, we show that a nickel catalyst promotes C−C coupling between glycosyl halides and aliphatic acids or primary amines (converted into redox‐active electrophiles in one step), in the presence of Hantzsch ester and LiI (or Et3N) under blue LED illumination to deliver C‐alkyl glycosides with high diastereoselectivity. Mechanistic studies support the photoinduced formation of alkyl radicals that react with a glycosyl nickel species generated in situ to facilitate cross‐coupling. Through this manifold, innate CO2H and NH2 motifs embedded within amino acids and oligopeptides are selectively capped and functionalized to afford glycopeptide conjugates through late‐stage glycosylation.

Interface Metal Oxides Regulating Electronic State around Nickel Species for Efficient Alkaline Hydrogen Electrocatalysis.

Heterogeneous electrocatalysis typically depends on the surface electronic states of active sites. Modulating the surface charge state of an electrocatalysts can be employed to improve performance. Among all the investigated materials, nickel (Ni)-based catalysts are the only non-noble-metal-based alternatives for both hydrogen oxidation and evolution reactions (HOR and HER) in alkaline electrolyte, while their activities should be further improved because of the unfavorable hydrogen adsorption behavior. Hereto, Ni with exceptional HOR electrocatalytic performance by changing the d-band center by metal oxides interface coupling formed in situ is endowed. The resultant MoO2 coupled Ni heterostructures exhibit an apparent HOR activity, even approaching to that of commercial 20% Pt/C benchmark, but with better long-term stability in alkaline electrolyte. An exceptional HER performance is also achieved by the Ni-MoO2 heterostructures. The experiment results are rationalized by the theoretical calculations, which indicate that coupling MoO2 with Ni results in the downshift of d-band center of Ni, and thus weakens hydrogen adsorption and benefits for hydroxyl adsorption. This concept is further proved by other metal oxides (e.g., CeO2 , V2 O3 , WO3 , Cr2 O3 )-formed Ni-based heterostructures to engineer efficient hydrogen electrocatalysts.

DFT Study of Mechanism and Stereochemistry of Nickel-Catalyzed trans-Arylative Desymmetrizing Cyclization of Alkyne-Tethered Malononitriles.

Present here is a density functional theory (DFT) study of the mechanism and origin of enantioselectivity of Ni-catalyzed desymmetric cyclization of alkyne-tethered malononitriles and aryl boronic acids. The reaction starts from transmetalation and arylnickel addition, followed by trans to cis isomerization to give cis-alkenyl nickel species. The stereodetermining step is the CN insertion, which prefers a transition state with the bystander CN group staying away from the ligand to reduce steric repulsion, and gives the final (R)-product.

Insight into the effect of CeO2 morphology on catalytic performance for steam reforming of glycerol

Shape-specific CeO2 nanocrystals (spheres, rods, cubes and nanoparticles) with well-defined crystal facets were successfully synthesized and used as the support to synthesize series Ni/CeO2. Ni/CeO2 was employed as the model catalysts to study the structure dependent behavior and reaction mechanism for hydrogen production from glycerol steam reforming (GSR). The metal-support interaction was finely tuned by altering the morphology of CeO2 support, which in turn affected the exposed specific surface area of nickel and oxygen vacancy concentration. The relationship between exposed surface area of active nickel as well as surface oxygen vacancies and catalytic performance was studied. Ni/CeO2-S with the mainly exposed (111) type planes obtained the strongest metal-support interaction. Electron effects due to the strong metal-support between nickel and cerium dioxide facilitated the formation of readily reducible nickel species (Niδ+). High nickel reduction and nickel dispersion contributed to the maximum active nickel exposure surface area, thus Ni/CeO2-S showed exceptional glycerol conversion. Meanwhile, the strong Ni-CeO2 interaction resulting in abundant oxygen vacancies that facilitated the dissociation of water to produce hydrogen, thus possessing a high H2 yield. Conversely, Ni/CeO2-NR and Ni/CeO2-NC have lower exposure areas and oxygen vacancy concentrations due to the different exposed crystal planes, and therefore have relatively poor catalytic activity. Moreover, the strong oxygen storage-release ability (CO-OSC-OSCC) promoted the oxidation of carbon deposition on Ni/CeO2-S. Additionally, carbon deposition was mainly the filamentous carbon growing towards the periphery, hence, Ni/CeO2-S obtained up to 25-h catalytic stability. The study of the regulatory role of Ni-CeO2 interaction on catalytic behavior can offer worthwhile direction for designing high-efficiency GSR catalysts.

Design of Hierarchically Tailored Hybrids Based on Nickle Nanocrystal-Decorated Manganese Dioxides for Enhanced Fire Safety of Epoxy Resin.

A novel and hierarchical hybrid composite (MnO2@CHS@SA@Ni) was synthesized utilizing manganese dioxide (MnO2) nanosheets as the core structure, self-assembly chitosan (CHS), sodium alginate (SA) and nickel species (Ni) as surface layers, and it was further incorporated into an epoxy matrix for achieving fire hazard suppression via surface self-assembly technology. Herein, the resultant hybrid epoxy composite possessed an exceptional nano-barrier and synergistic charring effect to aid the formation of a compact layered structure that enhanced its fire-resistive effectiveness. As a result, the addition of only 2 wt% MnO2@CHS@SA@Ni hybrids led to a dramatic reduction in the peak heat release rate and total heat release values (by ca. 33% and 27.8%) of the epoxy matrix. Notably, the peak smoke production rate and total smoke production values of EP/MnO2@CHS@SA@Ni 2% were decreased by ca. 16.9 and 38.4% compared to the corresponding data of pristine EP. This was accompanied by the suppression of toxic CO, NO release and the diffusion of thermal pyrolysis gases during combustion through TG-IR results. Overall, a significant fire-testing outcome of the proposed hierarchical structure was proven to be effective for epoxy composites in terms of flammability, smoke and toxicity reductions, optimizing their prospects in other polymeric materials in the respective fields.

Nickel(IV) Intermediates in Aminoquinoline-Directed C(sp2)-C(sp3) Coupling.

We use a ligand design strategy to isolate a cyclometalated nickel(IV) complex that is directly analogous to a key intermediate proposed in aminoquinoline-directed C-H functionalization catalysis. This nickel(IV) complex is formed by oxidative addition of a diaryliodonium reagent to an anionic nickel(II)-picolinate precursor. The nickel(IV) σ-aryl complex is stable at room temperature but undergoes C(sp2)-C(sp3) bond-forming reductive elimination under mild conditions (70 °C, 120 min). Overall, this study demonstrates the accessibility of long-sought-after nickel(IV) intermediates in C-H functionalization catalysis. Furthermore, it demonstrates that LX-type (bidentate, mono-anionic) ligands such as picolinate dramatically stabilize these nickel(IV) species.

Unravelling the Mechanism of Nickel Mediated Cross‐Electrophile‐ Electrophile Coupling Between Katritzky Salts and Acid Chlorides

AbstractModern nickel‐mediated cross‐electrophile coupling reactions devoid of organometallic nucleophiles have garnered a great deal of interest due to their ability to enhance functional group compatibility. Despite the recent advances in the field, various mechanistic pathways, such as radical chain and sequential oxidative addition, in addition to finding the active nickel species and reductant, render the reaction complex. Although the reduction of Ni(II) complexes by heterogeneous Mn could produce either Ni(I) or Ni(0) species, the latter is more generally proposed as an active species. Likewise, Ni(I) mediated reduction of pyridinium salts is commonly invoked to generate the transient alkyl radicals. In stark contrast, we present a comprehensive mechanistic examination and experimental evidence for the intermediacy of Ni(I) species, a synergistic reduction of pyridinium salts by Ni(I) and Mn. Using a combination of kinetic analysis, control experiments, and spectroscopic methods, the rate‐limiting reductive alkylation and resting state Ni(II) species have been identified.

Electrochemical and XPS investigations on the galvanic interaction between pentlandite and pyrrhotite in collectorless flotation system

Pentlandite and pyrrhotite are ubiquitously symbiotically aggregated with each other, and the galvanic interaction between them inevitably occurs in flotation process. However, there were few detailed researches regarding this galvanic interaction and its effect on the surface oxidation of pentlandite and pyrrhotite that has been reported. In this work, the galvanic interactions and its influence on the surface oxidation and collectorless flotation behaviors of pentlandite and pyrrhotite were systematically researched at pH 8.5. Results of electrochemical measurements showed that pentlandite had a higher OCP value than pyrrhotite, indicating that pentlandite would act as the cathode, while pyrrhotite acted as the anode in the galvanic couple. Compared to the minerals oxidized solely, a more passivated surface was found for both pentlandite and pyrrhotite. ICP-OES and XPS analyses demonstrated that in the presence of pyrrhotite, a thicker iron oxide/hydroxide film was obtained with a decrease in the species of sulfate and nickel oxide/hydroxide on pentlandite surface. For pyrrhotite, within the galvanic interaction, the oxidation and metal dissolution of pyrrhotite was accelerated. However, the hydrogen ion generated in the anodic reaction would hinder the precipitation of iron oxide/hydroxide and sulfate on pyrrhotite surface. Micro-flotation results further confirmed that the galvanic interaction between pentlandite and pyrrhotite significantly affected their collectorless flotation behaviors, which was also affected by the relative content ratio between them. This work systematically studied the galvanic interaction and its role in the surface oxidation in pentlandite/pyrrhotite collectorless flotation system, which could also provide reference for the further study on complex Ni-bearing sulfide minerals flotation.

Stepwise dispersion of nickel species for efficient coupling of electrocatalytic redox reactions

Advanced electrocatalysts are highly desirable to enhance energy conversion efficiency for properly coupling electrocatalytic redox reactions, but the fabrication of efficient bifunctional catalysts is still highly challenging. Herein, a self-feeding deposition strategy was demonstrated to disperse nickel species into single nickel atoms along with the growth of nitrogen-doped carbon nanotubes, thus inhibiting the thermal aggregation of nickel nanoparticles. The residual nickel nanoparticles are encapsulated among the bamboo-like carbon nanotubes and porous carbon matrix, which promotes the efficient electron transfer via the formation of heterojunctions. With the regulation of electronic and geometric structures between the single atom active sites and the isolated nickel nanoparticles, the unique nucleo- and electro-philic interfaces facilitate the targeted adsorption and activation of carbon dioxide and benzylamine molecules, respectively, thus narrowing the energy barriers to enhance electrocatalytic performances. The improved bifunctional electrocatalysis enables the carbon dioxide reduction into CO with an impressive Faraday efficiency (FE) up to 99.3 % and the highly efficient oxidation of benzylamine into benzonitrile (FE ∼ 98 %). This work not only reveals the fundamental understanding of the underlying structure–activity relationship, but also provides a new method for value-added chemicals production.

Catalytic Cyanation of C-N Bonds with CO2/NH3.

Cyanation of benzylic C-N bonds is useful in the preparation of important α-aryl nitriles. The first general catalytic cyanation of α-(hetero)aryl amines, analogous to the Sandmeyer reaction of anilines, was developed using reductive cyanation with CO2/NH3. A broad array of α-aryl nitriles was obtained in high yields and regioselectivity by C-N cleavage of intermediates as ammonium salts. Good tolerance of functional groups such as ethers, CF3, F, Cl, esters, indoles, and benzothiophenes was achieved. Using 13CO2, a 13C-labeled tryptamine homologue (five steps, 31% yield) and Cysmethynil (six steps, 37% yield) were synthesized. Both electronic and steric effects of ligands influence the reactivity of alkyl nickel species with electrophilic silyl isocyanates and thus determine the reactivity and selectivity of the cyanation reaction. This work contributes to the understanding of the controllable activation of CO2/NH3 and provides the promising potential of the amine cyanation reaction in the synthesis of bio-relevant molecules.

Enhanced Isopropyl Alcohol Conversion over Acidic Nickel Phosphate-Supported Zeolite Catalysts.

In this preliminary research, the catalytic activity of isopropyl alcohol conversion to diisopropyl ether through dehydration reaction catalyzed by zeolite-Ni and zeolite-Ni(H2PO4)2 was comparatively described. The natural zeolite was treated with 1% HF and 6 N HCl prior to modifications using the impregnation method. Isopropyl alcohol conversion was examined at a mild temperature of 150 °C for 3.5 h on the reflux system with various catalyst loadings. X-ray diffraction and Fourier transform infrared analysis confirmed the successful impregnation of nickel and nickel phosphate into the zeolite. Scanning electron microscopy analysis revealed a cubic-like structure on zeolite-Ni(H2PO4)2, whereas homogenously distributed nickel species were observed on the zeolite-Ni catalyst. Energy-dispersive X-ray spectroscopy analysis reinforced the accomplishment of zeolite modifications. The N2 physisorption isotherms showed a decline in the surface area and total pore volume of the zeolite because of the blocking of pores. The zeolite-Ni(H2PO4)2 catalyst had higher acidity than unmodified zeolite and zeolite-Ni catalysts, which inherently suggested that the presence of phosphate groups results in higher catalytic activity toward isopropyl alcohol. The highest catalytic activity was attained by 8 mEq/g metal loading zeolite-Ni(H2PO4)2 with isopropyl alcohol conversion of 81.51%, diisopropyl ether yield, and selectivity of 40.77 and 33.16%. The reusability study suggested that the zeolite-Ni(H2PO4)2 catalyst was still active and had sufficient catalytic activity stability toward isopropyl alcohol after the third cycle was reused. This nickel phosphate-based modified zeolite was adequately potential for diisopropyl ether production through isopropyl alcohol dehydration.

Appraisal of Ni Species Supported on Porous MgO during Ethanol Steam Reforming by XAS

AbstractOperando time‐resolved X‐ray absorption spectroscopy (XAS) was used to determine nickel species supported on porous MgO during the ethanol steam reforming reaction. The Principal Component Analysis (PCA) of the nickel K‐edge XAS spectra revealed Ni(OH)2, NiMgO, and metallic Ni during the activation and reaction of the catalysts. The Multivariate Curve Resolution‐Alternating Least Squares (MCR‐ALS) method for the time‐resolved XAS spectra data permitted to calculate the concentration of species during the activation and reaction steps and to determine the formation of NiMgO and nickel reduction degree. The samples prepared with surfactants, Ni10MgO‐F127 and Ni10MgO‐P123, showed less nickel reduction (less than 30 %) but were more active and stable than the reference Ni10MgO catalyst, which reduced 52 %. It happened due to the smaller particle size and a larger specific area of the porous supports. The samples synthesized without Pluronic deactivated, and ethanol dehydrogenation became predominant instead of the ethanol steam reforming.

Nickel Nanoparticles Decorated on Glucose-Derived Carbon Spheres as a Novel, Non-Palladium Catalyst for Epoxidation of Olefin

Carbon spheres supporting nickel nanoparticles (NPs), generated by the integration of hydrothermal and microwave irradiation techniques, catalyzed the epoxidation of 1-octene, cyclooctene, styrene, allyl alcohol, and cyclohexene. The average particle sizes of the carbon spheres (CSs) and nickel oxide species immobilized on the CSs were 240 nm and 26 nm, respectively. The fabricated composites incorporating nickel NPs showed higher activity in the cyclohexene epoxidation process. The cyclohexene conversion was enhanced by raising the Ni loading to 10%. Within 14 h, the cyclohexene conversion had grown to 98%. This robust catalytic activity can be attributed to the efficient distribution of Ni species on the CSs, the facile lowering of the surface, and the development of uniformly nanosized species. The composite exhibited good recyclability across at least five cycles (which is not a simple task involving nickel-nanoparticle-based catalysts that are employed in water), and no nickel species leached into the solution, making the total system environmentally benign and cost-effective.

Three-component enantioselective alkenylation of organophosphonates via nickel metallaphotoredox catalysis

•Highly enantioselective synthesis of structurally complex chiral phosphonates •Modular and stereodivergent access to chiral trans- and cis-alkenyl moieties •Asymmetric radical multicomponent reaction via metallaphotoredox catalysis •Enantioselective control of alkyl radicals by guiding the trajectory of radical metalation The development of efficient catalytic multicomponent reactions (MCRs) is highly sought-after in chemical synthesis. However, catalytic asymmetric MCRs, particularly involving radical species, remain largely underdeveloped due to the exceptionally high reactivity of open-shell radical species. Herein, we report a metallaphotoredox-catalyzed asymmetric three-component method to access a diverse array of enantio-enriched α-alkenyl phosphonates from readily available vinyl phosphonates, alkenyl halides, and alkyl trifluoroborates under mild conditions. This operationally simple and redox-neutral protocol exhibits broad substrate scope and excellent chemo-, regio-, stereo-, and enantioselectivity. Furthermore, by simple modification of the triplet energy of the photocatalyst employed, both enantio-enriched trans and cis α-alkenyl phosphonates can be divergently accessed. Detailed computational and experimental studies were undertaken to elucidate the mechanism and origin of the observed reactivity and selectivity, which support a radical cascade sequence with α-phosphonate controlling the trajectory of radical capture by a chiral tetrahedral alkenyl nickel(II) species in the enantioselectivity-determining step. The development of efficient catalytic multicomponent reactions (MCRs) is highly sought-after in chemical synthesis. However, catalytic asymmetric MCRs, particularly involving radical species, remain largely underdeveloped due to the exceptionally high reactivity of open-shell radical species. Herein, we report a metallaphotoredox-catalyzed asymmetric three-component method to access a diverse array of enantio-enriched α-alkenyl phosphonates from readily available vinyl phosphonates, alkenyl halides, and alkyl trifluoroborates under mild conditions. This operationally simple and redox-neutral protocol exhibits broad substrate scope and excellent chemo-, regio-, stereo-, and enantioselectivity. Furthermore, by simple modification of the triplet energy of the photocatalyst employed, both enantio-enriched trans and cis α-alkenyl phosphonates can be divergently accessed. Detailed computational and experimental studies were undertaken to elucidate the mechanism and origin of the observed reactivity and selectivity, which support a radical cascade sequence with α-phosphonate controlling the trajectory of radical capture by a chiral tetrahedral alkenyl nickel(II) species in the enantioselectivity-determining step.

Boosting CO2 hydrogenation to methane over Ni-based ETS-10 zeolite catalyst.

The activation and conversion of the CO2 molecule have always been the most vexing challenge due to its chemical inertness. Developing highly active catalysts, which could overcome dynamic limitations, has emerged as a provable and effective method to promote CO2 activation–conversion. Herein, ETS-10 zeolite–based catalysts, with active nickel species introduced by in situ doping and impregnation, have been employed for CO2 methanation. Conspicuous CO2 conversion (39.7%) and perfect CH4 selectivity (100%) were achieved over the Ni-doped ETS-10 zeolite catalyst at 280°C. Comprehensive analysis, which include X-ray diffraction, N2 adsorption–desorption, SEM, TEM, H2 chemisorption, CO2 temperature programmed desorption, and X-ray photoelectron spectroscopy, was performed. Also, the results indicated that the resultant hierarchical structure, high metal dispersion, and excellent CO2 adsorption–activation capacity of the Ni-doped ETS-10 zeolite catalyst played a dominant role in promoting CO2 conversion and product selectivity.

Β-Feooh Nanorods As a Highly Active Self-Repairing Anode Catalyst for Alkaline Water Electrolysis Powered By Renewable Energy

The use of renewable energy as a primary energy source is urged because of the rapid progress of global warming. Because the renewable energy is unevenly distributed in terms of place and time, the production of hydrogen from renewable energy is crucial. Alkaline water electrolysis is a cost-effective technology for this purpose, though the degradation of electrodes under fluctuating power of renewable energy is recently regarded as a crucial problem. We have recently reported that a in-situ repair of anode catalyst (self-repairing catalyst), supplying fresh catalyst from electrolyte is quite useful to improve the lifetime under unsteady operation [1]. A hybrid cobalt hydroxide nanosheet (Co-ns) was used as the self-repairing catalyst, whereas its electrocatalytic activity is moderate. In this study, we demonstrate the use of β-FeOOH nanorods (β-FeOOH-nr) as a highly active and durable self-repairing catalyst. Because β-FeOOH-nr consists of iron as a metallic element, it is promising for its low cost and resource abundance. β-FeOOH-nr was synthesized by the coprecipitation of Fe3+ with tris(hydroxymethyl)aminomethane, followed by heating at 80 °C. The width and length of β-FeOOH-nr were 3–6 nm and 4–200 nm, respectively. The Fe K-edge XANES analysis showed that β-FeOOH-nr consists of Fe3+ species. Electrochemical tests were performed in a three-electrode PFA cell, using a nickel wire, a nickel coil, and a reversible hydrogen electrode, as working, counter, and reference electrodes, respectively. The β-FeOOH-nr was dispersed in 1 M KOH as an electrolyte. β-FeOOH-nr was first deposited on the nickel wire electrode by constant current electrolysis at 1 A·cm–2 for 240 min (30 min × 8 cycles). β-FeOOH-nr formed a thin layer of bundled nanorods and exhibited the oxygen evolution reaction (OER) overpotential of 320 mV at 100 mA cm–2, while previously reported Co-ns exhibited 342 mV. In addition, the activation of β-FeOOH-nr-coated electrode is almost finished at the first 30 min of the electrolysis, whereas Co-ns required 240 min for the activation. Because β-FeOOH-nr-coated electrode exhibited high OER activity with a small amount of β-FeOOH-nr deposited on the electrode, β-FeOOH-nr could activate electrode with shorted electrolysis time. The β-FeOOH-nr-coated electrode indicated the redox peak due to Ni2+/Ni3+ at 1.44 V vs. RHE which is at higher potential than that of a bare nickel electrode, implying that β-FeOOH-nr formed composite with active nickel species, such as Ni(OH)2 as highly active materials. The durability of the catalyst-coated electrode was examined in the presence of β-FeOOH-nr in the electrolyte by the newly reported shutdown-based accelerated durability test (SD-ADT) [2]. SD-ADT consists of multiple cycles of constant current electrolysis at 600 mA·cm–2 for 1 min and potential retainment at low potential of 0.5 V vs. RHE for 1 min. A bare nickel electrode is degraded only within 50 cycles by the SD-ADT (OER overpotential reached 640 mV at the 200th cycle), whereas β-FeOOH-nr-coated nickel electrode retained its low OER overpotential of 285 mV in at least 4000 cycles. Comparing with the SD-ADT in the absence of β-FeOOH-nr in the electrolyte, it was shown that β-FeOOH-nr was deposited during the SD-ADT to repair degraded electrode. In conclusion, β-FeOOH-nr was shown to be a useful anode catalyst for alkaline water electrolysis powered by fluctuating renewable energy. By dispersing β-FeOOH-nr in an electrolyte, the alkaline water electrolyzer can establish self-repairing system with very long lifetime under frequent potential change. The synchrotron radiation experiments were performed at the BL16B2 of SPring-8 with approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal No. 2021A5310). This work was supported by the JSPS KAKENHI (grant number 20H02821) from Ministry of Education, Culture, Sports, Science and Technology (MEXT) Japan. Part of this study uses outcomes of the development of fundamental technology for the advancement of water electrolysis hydrogen production in the advancement of hydrogen technologies and utilization projects (grant number JPNP14021) commissioned by the New Energy and Industrial Technology Development Organization (NEDO) in Japan.

Production of Monoethylene Glycol from Lignocellulosic Biomass via Catalytic Hydrogenation: A Review

Ethane and ethanol are produced through steam cracking and fermentation into ethylene respectively, which is then hydrolysed into monoethylene glycol (MEG). The disadvantages of both processes included used of easily oxidized substance and large quantities of water in order to minimize by-products such as diethylene glycol and triethylene glycol. Apart from that, MEG can also be produced by catalytic hydrogenation of biomass at extreme temperature and pressure with presence of catalyst. At the same time, this process uses lignocellulosic waste that have a high cellulose content such as residues from the agricultural and food industries. However, lignocellulosic biomass has to be treated to remove lignin content that may lower the rate of hydrogenation activity. In addition, most studies have found that the temperature in range of 240 °C to 280 °C and pressure of 5 MPa to 6 MPa are able to produce 18 wt% to 64 wt% of MEG. Meanwhile, the catalyst that have attract the researchers’ attention are nickel and tungsten species which are able to increase the MEG yield by overcoming the activation energy of the hydrogenation process. Factors such as lignocellulose’s pre-treatment, operating temperature and pressure, and the presence of catalyst will be discussed further.

The direct synthesis of Ni/SAPO-11 hydroisomerization catalyst via a novel two-step crystallization strategy

The Ni/SAPO-11 catalyst used for n-hexane hydroisomerization was prepared via a novel two-step crystallization strategy. It involves introduction of nickel salt into the pre-crystalized system of SAPO-11 by grinding followed by a second crystallization step. No extra solvent is introduced during the whole synthesis procedure which reduces waste liquid emissions significantly. More importantly, interaction between nickel and support is effectively regulated by the novel method to achieve a well dispersed nickel species and inhibit formation of inert nickel spinel simultaneously. Chemical environments of framework Si are tuned to enhance surface acidity of the Ni/SAPO-11 catalyst. It also shows smaller particle size which favors fast diffusion of reactants and products. Insights into the two-step crystallization indicate that accumulation of SAPO-11 precursors in the pre-crystallization stage, pH regulation by nickel salt and structural directing effect of Ni2+ during the second crystallization period account for the rapid crystal growth and smaller particle size of the Ni/SAPO-11 catalyst. All the unique features endow the Ni/SAPO-11 catalyst higher activity and isomers selectivity than the Pt/SAPO-11 catalyst in n-hexane hydroisomerization.

Electrochemically embedded nickel oxide in a highly porous manganese oxide film with enhanced catalytic kinetics of the urea oxidation reaction

The use of well-dispersed nickel catalysts with atomic-scale sizes is an effective approach for maximizing catalytic activity and selectivity for the urea oxidation reaction (UOR). Herein, a porous ultrathin film of Birnessite-type manganese oxide is anodically deposited on a nickel substrate as a catalyst support. Some of the intercalated sodium ions are replaced by the dissolved nickel ions from the nickel substrate in the anodic process, forming manganese oxide with partially intercalated nickel ions (denoted MnO2). The amount of nickel species can be easily increased by cyclic voltammetry in the nickel sulfate electrolyte (denoted MnO2-Ni), without the relatively time-consuming process of conventional ion exchange. Most of the embedded nickel species are catalytic Ni3+ ions, rendering MnO2-Ni a favorable catalyst to boost the UOR. The cyclic voltammetry results reveal that Ni3+ catalysts, when inserted into the layer-structured manganese oxide, can increase the electroactive surface area for the adsorption of urea and increase the charge-transfer rate constant for the Ni3+/Ni2+ redox couple, leading to an improved catalytic rate constant of the UOR. A highly porous manganese oxide matrix provides many transport pathways for facilitating UOR kinetics. Electrochemical impedance spectroscopy shows that MnO2-Ni has lower direct and indirect UOR impedances than MnO2 and bare Ni electrodes, leading to a greater oxidation current and lower onset potential.

Manipulating the morphology and the electronic structures of nickel-cobalt selenides@N-doped carbon for aqueous alkaline batteries

Morphology engineering and surface modification are efficient approaches to enhance the electrochemical performance of transition metal chalcogenides. In the present work, (Ni,Co)Se2@N-doped carbon with different morphologies derived from Prussian blue analogous were synthesized. The influence of chemical etching on the morphology, electronic structure and electrochemical performance and activity of (Ni,Co)Se2@N-doped carbon were investigated. The results demonstrated that the chemical etching not only resulted in increased proportion of metal ions with low oxidation states, but also caused the reduction of the nickel and cobalt species on the surface. Therefore, better reversibility and enhanced reaction kinetics were observed in (Ni,Co)Se2@N-doped carbon nanocages despite that the resultant nanocubes showed higher specific capacity (432.1 C g−1 at 0.5 mA cm−2). Moreover, an aqueous alkaline battery was assembled by integrating commercial activated carbon and (Ni,Co)Se2@N-doped carbon nanocubes as negative and positive electrode, respectively, which could reach a working voltage of 1.65 V and achieve an energy density of 28.2 W h kg−1 at 307 W kg−1 and remain 18.5 W h kg−1 at 3.07 kW kg−1. Our study on (Ni,Co)Se2@N-doped carbon provides helpful inspiration to design nickel-cobalt selenides with excellent electrochemical performance as active materials for aqueous alkaline batteries.