Large-scale industrial application of electrolytic splitting of water has called for the development of oxygen evolution electrodes that are inexpensive, robust and can deliver large current density (>500 mA cm−2) at low applied potentials. Here we show that an efficient oxygen electrode can be developed by electrodepositing amorphous mesoporous nickel–iron composite nanosheets directly onto macroporous nickel foam substrates. The as-prepared oxygen electrode exhibits high catalytic activity towards water oxidation in alkaline solutions, which only requires an overpotential of 200 mV to initiate the reaction, and is capable of delivering current densities of 500 and 1,000 mA cm−2 at overpotentials of 240 and 270 mV, respectively. The electrode also shows prolonged stability against bulk water electrolysis at large current. Collectively, the as-prepared three-dimensional structured electrode is the most efficient oxygen evolution electrode in alkaline electrolytes reported to the best of our knowledge, and can potentially be applied for industrial scale water electrolysis.
Two-dimensional metal-organic frameworks represent a family of materials with attractive chemical and structural properties, which are usually prepared in the form of bulk powders. Here we show a generic approach to fabricate ultrathin nanosheet array of metal-organic frameworks on different substrates through a dissolution–crystallization mechanism. These materials exhibit intriguing properties for electrocatalysis including highly exposed active molecular metal sites owning to ultra-small thickness of nanosheets, improved electrical conductivity and a combination of hierarchical porosity. We fabricate a nickel-iron-based metal-organic framework array, which demonstrates superior electrocatalytic performance towards oxygen evolution reaction with a small overpotential of 240 mV at 10 mA cm−2, and robust operation for 20,000 s with no detectable activity decay. Remarkably, the turnover frequency of the electrode is 3.8 s−1 at an overpotential of 400 mV. We further demonstrate the promise of these electrodes for other important catalytic reactions including hydrogen evolution reaction and overall water splitting.
Polynary single‐atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces. However, the fabrication and identification of such an active‐site prototype remain elusive. Here we report isolated diatomic Ni‐Fe sites anchored on nitrogenated carbon as an efficient electrocatalyst for CO2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 % over a wide potential range from −0.5 to −0.9 V (98 % at −0.7 V), and robust durability, retaining 99 % of its initial selectivity after 30 hours of electrolysis. Density functional theory studies reveal that the neighboring Ni‐Fe centers not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO, but also undergo distinct structural evolution into a CO‐adsorbed moiety upon CO2 uptake.
3515wileyonlinelibrary.com OER and HER catalysts based on the earth-abundant fi rst row transition metals (Fe, Co, and Ni, etc.) has received extensive research interest. [9][10][11][12][13] Although signifi cant progress has been achieved, great challenges remain for nonprecious catalysts to achieve activity and stability that are comparable to conventional precious metals. To this end, one promising approach is to develop multimetallic/carbon catalysts by taking advantage of abundant metal-metal and metal-carbon synergistic interactions to enhance the performance of nonprecious catalysts. [14][15][16] The NiFe (oxy)hydroxide-based catalysts are regarded as one of the best performing nonprecious OER electrocatalysts in alkaline solutions, [17][18][19][20][21] which can be synthesized by coupling with carbon nanotube or graphene to achieve better conductivity and synergistic effects via hydrothermal, [ 19,22 ] or electrodeposition onto gold, glassy carbon, and nickel foam, etc., conductive current collector substrates. [ 19,23,24 ] The high OER activities of NiFe catalysts are generally attributed to a strong synergistic effect upon the incorporation of Fe, even in trace amount, into NiOOH, although the complete mechanisms and structural characteristics are not yet fully understood. [ 19,23 ] NiFe catalysts also have been reported for HER in alkaline media, [ 25 ] although the synergistic effect for HER is not as signifi cant as that for OER, and the reported activity for HER is relatively low compared to state-of-the-art nonprecious HER catalysts. Nevertheless, using the same catalyst as both the anode and cathode in an electrolysis device is very attractive, which could not only signifi cantly improve the integration and simplifi cation of the water splitting system, but also provide the feasibility of industrial application of water splitting technology.Besides having an effi cient catalyst, rational design of catalyst structure is known to be crucial for improving the electrode performance. In pursuit of creating large surface area and high active site density, various attempts have been devoted to developing 3D nanostructured catalyst materials, [26][27][28] such as mesoporous NiFe nanosheets, [ 24 ] NiCo 2 O 4 nanosheets/halloysite nanotubes, [ 26 ] hierarchically structured carbon microfi bre, [ 29 ] and multilayered TiO 2 nanowire arrays. [ 30 ] Moreover, smart design of a catalyst with macroscopic structure onto conductive porous support (e.g., nickel foam) could afford Bifunctional Porous NiFe/NiCo 2 O 4 /Ni Foam Electrodes with Triple Hierarchy and Double Synergies for Effi cient Whole Cell Water SplittingChanglong Xiao , Yibing Li , Xunyu Lu , and Chuan Zhao * A 3D hierarchical porous catalyst architecture based on earth abundant metals Ni, Fe, and Co has been fabricated through a facile hydrothermal and electrodeposition method for effi cient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The electrode is comprised of three levels of porous structures including the bottom su...
Exploiting the valley degree of freedom to store and manipulate information provides a novel paradigm for future electronics. A monolayer transition-metal dichalcogenide (TMDC) with a broken inversion symmetry possesses two degenerate yet inequivalent valleys, which offers unique opportunities for valley control through the helicity of light. Lifting the valley degeneracy by Zeeman splitting has been demonstrated recently, which may enable valley control by a magnetic field. However, the realized valley splitting is modest (∼0.2 meV T). Here we show greatly enhanced valley spitting in monolayer WSe, utilizing the interfacial magnetic exchange field (MEF) from a ferromagnetic EuS substrate. A valley splitting of 2.5 meV is demonstrated at 1 T by magnetoreflectance measurements and corresponds to an effective exchange field of ∼12 T. Moreover, the splitting follows the magnetization of EuS, a hallmark of the MEF. Utilizing the MEF of a magnetic insulator can induce magnetic order and valley and spin polarization in TMDCs, which may enable valleytronic and quantum-computing applications.
Large-scale storage of renewable energy in the form of hydrogen (H2) fuel via electrolytic water splitting requires the development of water oxidation catalysts that are efficient and abundant. Carbon-based nanomaterials such as carbon nanotubes have attracted significant applications for use as substrates for anchoring metal-based nanoparticles. We show that, upon mild surface oxidation, hydrothermal annealing and electrochemical activation, multiwall carbon nanotubes (MWCNTs) themselves are effective water oxidation catalysts, which can initiate the oxygen evolution reaction (OER) at overpotentials of 0.3 V in alkaline media. Oxygen-containing functional groups such as ketonic C═O generated on the outer wall of MWCNTs are found to play crucial roles in catalyzing OER by altering the electronic structures of the adjacent carbon atoms and facilitates the adsorption of OER intermediates. The well-preserved microscopic structures and highly conductive inner walls of MWCNTs enable efficient transport of the electrons generated during OER.
Efficient generation of hydrogen from water-splitting is an underpinning chemistry to realize the hydrogen economy. Low cost, transition metals such as nickel and iron-based oxides/hydroxides have been regarded as promising catalysts for the oxygen evolution reaction in alkaline media with overpotentials as low as ~200 mV to achieve 10 mA cm−2, however, they are generally unsuitable for the hydrogen evolution reaction. Herein, we show a Janus nanoparticle catalyst with a nickel–iron oxide interface and multi-site functionality for a highly efficient hydrogen evolution reaction with a comparable performance to the benchmark platinum on carbon catalyst. Density functional theory calculations reveal that the hydrogen evolution reaction catalytic activity of the nanoparticle is induced by the strong electronic coupling effect between the iron oxide and the nickel at the interface. Remarkably, the catalyst also exhibits extraordinary oxygen evolution reaction activity, enabling an active and stable bi-functional catalyst for whole cell water-splitting with, to the best of our knowledge, the highest energy efficiency (83.7%) reported to date.
Eighteen protic ionic liquids containing different combinations of cations and anions, hydrophobicity, viscosity, and conductivity have been synthesized and their physicochemical properties determined. In one series, the diethanolammonium cations were combined with acetate, formate, hydrogen sulfate, chloride, sulfamate, and mesylate anions. In the second series, acetate and formate anions were combined with amine bases, triethylamine, diethylamine, triethanolamine, di-n-propylamine, and di-n-butylamine. The electrochemical characteristics of the eight protic ionic liquids that are liquid at room temperature (RTPILs) have been determined using cyclic, microelectrode, and rotating disk electrode voltammetries. Potential windows of the RTPILs have been compared at glassy carbon, platinum, gold, and boron-doped diamond electrodes and generally found to be the largest in the case of glassy carbon. The voltammetry of IUPAC recommended potential scale reference systems, ferrocene/ferrocenium and cobaltocenium/cobaltocene, have been evaluated and found to be ideal in the case of the less viscous RTPILs but involve adsorption in the highly viscous ones. Other properties such as diffusion coefficients, ionic conductivity, and double layer capacitance also have been measured. The influence of water on the potential windows, viscosity, and diffusion has been studied systematically by deliberate addition of water to the dried ionic liquids. The survey highlights the problems with voltammetric studies in highly viscous room temperature protic ionic liquids and also suggests the way forward with respect to their possible industrial use.
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