Bimetallic nickel-cobalt hydrides in H2 activation and catalytic proton reduction.
ABSTRACT: The synergism of the electronic properties of nickel and cobalt enables bimetallic NiCo complexes to process H2. The nickel-cobalt hydride [(dppe)Ni(pdt)(H)CoCp*]+ ([1H]+ ) arising from protonation of the reduced state 1 was found to be an efficient electrocatalyst for H2 evolution with Cl2CHCOOH, and the oxidized [Ni(ii)Co(iii)]2+ form is capable of activating H2 to produce [1H]+ . The features of stereodynamics, acid-base properties, redox chemistry and reactivity of these bimetallic NiCo complexes in processing H2 are potentially related to the active site of [NiFe]-H2ases.
Project description:The rational design of nickel-based cathodes with highly ordered micro-nano hierarchical architectures by a facile process is fantastic but challenging to achieve for high-capacity and high-rate Ni-Zn batteries. Herein, a one-step etching-deposition-growth process is demonstrated to prepare hierarchical micro-nano sheet arrays for Ni-Zn batteries with outstanding performance and high rate. The fabrication process is conducted at room temperature without any need of heating and stirring, and the as-grown nickel-cobalt double hydroxide (NiCo-DH) supported on conductive nickel substrate is endowed with a unique 3D hierarchical architecture of micro-nano sheet arrays, which empower the effective exposure of active materials, easy electrolyte access, fast ion diffusion, and rapid electron transfer. Benefiting from these merits in combination, the NiCo-DH electrode delivers a high specific capacity of 303.6 mAh g<sup>-1</sup> and outstanding rate performance (80% retention after 20-fold current increase), which outperforms the electrodes made of single Ni(OH)<sub>2</sub> and Co(OH)<sub>2</sub>, and other similar materials. The NiCo-DH electrode, when employed as the cathode for a Ni-Zn battery, demonstrates a high specific capacity of 329 mAh g<sup>-1</sup>. Moreover, the NiCo-DH//Zn battery also exhibits high electrochemical energy conversion efficiency, excellent rate capability (62% retention after 30-fold current increase), ultrafast charge characteristics, and strong tolerance to the high-speed conversion reaction.
Project description:The intermediacy of a reduced nickel-iron hydride in hydrogen evolution catalyzed by Ni-Fe complexes was verified experimentally and computationally. In addition to catalyzing hydrogen evolution, the highly basic and bulky (dppv)Ni(?-pdt)Fe(CO)(dppv) ((0); dppv = cis-C2H2(PPh2)2) and its hydride derivatives have yielded to detailed characterization in terms of spectroscopy, bonding, and reactivity. The protonation of (0) initially produces unsym-[H1](+), which converts by a first-order pathway to sym-[H1](+). These species have C1 (unsym) and Cs (sym) symmetries, respectively, depending on the stereochemistry of the octahedral Fe site. Both experimental and computational studies show that [H1](+) protonates at sulfur. The S = 1/2 hydride [H1](0) was generated by reduction of [H1](+) with Cp*2Co. Density functional theory (DFT) calculations indicate that [H1](0) is best described as a Ni(I)-Fe(II) derivative with significant spin density on Ni and some delocalization on S and Fe. EPR spectroscopy reveals both kinetic and thermodynamic isomers of [H1](0). Whereas [H1](+) does not evolve H2 upon protonation, treatment of [H1](0) with acids gives H2. The redox state of the "remote" metal (Ni) modulates the hydridic character of the Fe(II)-H center. As supported by DFT calculations, H2 evolution proceeds either directly from [H1](0) and external acid or from protonation of the Fe-H bond in [H1](0) to give a labile dihydrogen complex. Stoichiometric tests indicate that protonation-induced hydrogen evolution from [H1](0) initially produces (+), which is reduced by [H1](0). Our results reconcile the required reductive activation of a metal hydride and the resistance of metal hydrides toward reduction. This dichotomy is resolved by reduction of the remote (non-hydride) metal of the bimetallic unit.
Project description:Rational design of metal compounds in terms of the structure/morphology and chemical composition is essential to achieve desirable electrochemical performances for fast energy storage because of the synergistic effect between different elements and the structure effect. Here, an approach is presented to facilely fabricate mixed-metal compounds including hydroxides, phosphides, sulfides, oxides, and selenides with well-defined hollow nanocage structure using metal-organic framework nanocrystals as sacrificial precursors. Among the as-synthesized samples, the porous nanocage structure, synergistic effect of mixed metals, and unique phosphide composition endow nickel cobalt bimetallic phosphide (NiCo-P) nanocages with outstanding performance as a battery-type Faradaic electrode material for fast energy storage, with ultrahigh specific capacity of 894 C g<sup>-1</sup> at 1 A g<sup>-1</sup> and excellent rate capability, surpassing most of the reported metal compounds. Control experiments and theoretical calculations based on density functional theory reveal that the synergistic effect between Ni and Co in NiCo-P can greatly increase the OH<sup>-</sup> adsorption energy, while the hollow porous structure facilitates the fast mass/electron transport. The presented work not only provides a promising electrode material for fast energy storage, but also opens a new route toward structural and compositional design of electrode materials for energy storage and conversion.
Project description:A unique three-dimensional (3D) structure consisting of a hierarchical nickel-cobalt dichalcogenide spinel nanostructure is investigated for its electrocatalytic properties at benign neutral and alkaline pH and applied as an air cathode for practical zinc-air batteries. The results show a high oxygen evolution reaction catalytic activity of nickel-cobalt sulfide nanosheet arrays grown on carbon cloth (NiCo<sub>2</sub>S<sub>4</sub> NS/CC) over the commercial benchmarking catalyst under both pH conditions. In particular, the NiCo<sub>2</sub>S<sub>4</sub> NS/CC air cathode shows high discharge capacity, a narrow potential gap between discharge and charge, and superior cycle durability with reversibility, which exceeds that of commercial precious metal-based electrodes. The excellent performance of NiCo<sub>2</sub>S<sub>4</sub> NS/CC in water electrolyzers and zinc-air batteries is mainly due to highly exposed electroactive sites with a rough surface, morphology-based advantages of nanosheet arrays, good adhesion between NiCo<sub>2</sub>S<sub>4</sub> and the conducting carbon cloth, and the active layer formed of nickel-cobalt (oxy)hydroxides during water splitting. These results suggest that NiCo<sub>2</sub>S<sub>4</sub> NS/CC could be a promising candidate as an efficient electrode for high-performance water electrolyzers and rechargeable zinc-air batteries.
Project description:A nickel(II) porphyrin Ni-P (P=porphyrin) bearing four meso-C6 F5 groups to improve solubility and activity was used to explore different hydrogen-evolution-reaction (HER) mechanisms. Doubly reduced Ni-P ([Ni-P](2-) ) was involved in H2 production from acetic acid, whereas a singly reduced species ([Ni-P](-) ) initiated HER with stronger trifluoroacetic acid (TFA). High activity and stability of Ni-P were observed in catalysis, with a remarkable ic /ip value of 77 with TFA at a scan rate of 100?mV?s(-1) and 20?°C. Electrochemical, stopped-flow, and theoretical studies indicated that a hydride species [H-Ni-P] is formed by oxidative protonation of [Ni-P](-) . Subsequent rapid bimetallic homolysis to give H2 and Ni-P is probably involved in the catalytic cycle. HER cycling through this one-electron-reduction and homolysis mechanism has been proposed previously but rarely validated. The present results could thus have broad implications for the design of new exquisite cycles for H2 generation.
Project description:The ferrous dithiolato carbonyl Fe(S(2)C(3)H(6))(CO)(2)(dppe) (1) condenses with NiCl(2)(dppe) to give [FeNi(pdt)(mu-Cl)(CO)(dppe)(2)]BF(4) ([2Cl](+)). The corresponding reaction of the ditosylate Ni(OTs)(2)(dppe) gave the dication [(CO)(2)(dppe)Fe(pdt)Ni(dppe)](OTs)(2) ([2(CO)](OTs)(2)) (pdt = 1,3-propanedithiolate; dppe = 1,2-C(2)H(4)(PPh(2))(2); OTs(-) = CH(3)C(6)H(4)-4-SO(3)(-)). Reduction of the bimetallic dicarbonyl with borohydride salts afforded impure, thermally stable hydride, [(CO)(dppe)Fe(pdt)(mu-H)Ni(dppe)](+) ([2H](+)). A reliable route to NiFe(SR)(2)H species entailed protonation of (CO)(3)Fe(pdt)Ni(dppe) to give [(CO)(3)Fe(pdt)(mu-H)Ni(dppe)](+) ([3H](+)). The iron-nickel dithiolato hydride, [3H]BF(4), was characterized crystallographically: as anticipated by biophysical studies, the hydride ligand is bridging, the Fe center is octahedral, and the Ni center is pentacoordinate. Solutions of [3H]BF(4) undergo substitution by dppe to give [2H](+). The hydride undergoes rapid deprotonation and is an electrocatalyst for hydrogen evolution from trifluoroacetic acid. Oxidation of 3 gives a mixed valence species (+), a potential model for the Ni-L state.
Project description:Nickel iron oxide is considered a benchmark nonprecious catalyst for the oxygen evolution reaction (OER). However, the nature of the active site in nickel iron oxide is heavily debated. Here we report direct spectroscopic evidence for the different active sites in Fe-free and Fe-containing Ni oxides. Ultrathin layered double hydroxides (LDHs) were used as defined samples of metal oxide catalysts, and 18 O-labeling experiments in combination with in?situ Raman spectroscopy were employed to probe the role of lattice oxygen as well as an active oxygen species, NiOO- , in the catalysts. Our data show that lattice oxygen is involved in the OER for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. Moreover, NiOO- is a precursor to oxygen for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. These data indicate that bulk Ni sites in Ni and NiCo oxides are active and evolve oxygen via a NiOO- precursor. Fe incorporation not only dramatically increases the activity, but also changes the nature of the active sites.
Project description:We report a wire-shaped three-dimensional (3D)-hybrid supercapacitor with high volumetric capacitance and high energy density due to an interconnected 3D-configuration of the electrode allowing for large number of electrochemical active sites, easy access of electrolyte ions, and facile charge transport for flexible wearable applications. The interconnected and compact electrode delivers a high volumetric capacitance (gravimetric capacitance) of 73 F cm<sup>-3</sup> (2446 F g<sup>-1</sup>), excellent rate capability, and cycle stability. The 3D-nickel cobalt-layered double hydroxide onto 3D-nickel wire (NiCo LDH/3D-Ni)//the 3D-manganese oxide onto 3D-nickel wire (Mn<sub>3</sub>O<sub>4</sub>/3D-Ni) hybrid supercapacitor exhibits energy density of 153.3 Wh kg<sup>-1</sup> and power density of 8810 W kg<sup>-1</sup>. The red light-emitting diode powered by the as-prepared hybrid supercapacitor can operate for 80 min after being charged for tens of seconds and exhibit excellent electrochemical stability under various deformation conditions. The results verify that such wire-shaped 3D-hybrid supercapacitors are promising alternatives for batteries with long charge-discharge times, for smart wearable and implantable devices.
Project description:NiCo nanoalloy (4-6?nm) encapsulated in grapheme layers (NiCo@G) has been prepared by thermolysis of a 3D bimetallic complex CoCo[Ni(EDTA)]2·4H2O and successfully employed as a catalyst to improve the dehydrogenation performances of LiAlH4 by solid ball-milling. NiCo@G presents a superior catalytic effect on the dehydrogenation of LiAlH4. For LiAlH4 doped with 1?wt% NiCo@G (LiAlH4-1?wt% NiCo@G), the onset dehydrogenation temperature of LiAlH4 is as low as 43?°C, which is 109?°C lower than that of pristine LiAlH4. 7.3?wt% of hydrogen can be released from LiAlH4-1?wt% NiCo@G at 150?°C within 60?min. The activation energies of LiAlH4 dehydrogenation are extremely reduced by 1?wt% NiCo@G doping.
Project description:Global warming remains one of the greatest challenges. One of the most prominent solutions is to close the carbon cycle by utilizing the greenhouse gas: CO<sub>2,</sub> and CH<sub>4</sub>, as a feedstock via the dry reforming of methane (DRM). This work provided an insight into how the NiCo bimetallic catalyst can perform with high stability against coking during DRM compared to the Ni and Co monometallic catalysts, in which the experimental and computational techniques based on density functional theory were performed. It was found that the high stability against coking found on the NiCo surface can be summarized into two key factors: (1) the role of Co weakening the bond between a Ni active site and coke (2) significantly high surface coke diffusion rate on NiCo. Moreover, the calculation of the surface fraction weighted rate of coke diffusion which modeled the real NiCo particle into four regions: Ni-dominant, Co-dominant, NiCo-dominant, and the mixed region consisting a comparable amount of the former there regions, have shown that the synthesis of a NiCo particle should be dominated with NiCo region while keeping the Ni-dominant, and Co-dominant regions to be as low as possible to facilitate coke diffusion and removal. Thus, to effectively utilize the coke-resistant property of NiCo catalyst for DRM, one should together combine its high coke diffusion rate with coke removal mechanisms such as oxidation or hydrogenation, especially at the final diffusion site, to ensure that there will not be enough coke at the final site that will cause back-diffusion.