NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript>/rGO hybrid nanostructures for efficient electrocatalytic oxygen evolution

We report the synthesis of NiCo₂O₄/reduced graphene oxide (NiCo₂O₄/rGO) hybrid hierarchical structures with unique nanonet and microsphere morphologies by organic polar solvent-assisted solvothermal method. The electrocatalytic oxygen evolution reaction (OER) activity of these materials is studied by cyclic voltammetry, linear sweep voltammetry and chronoamperometry methods in O₂-saturated 0.1 M KOH solution. The NiCo₂O₄/rGO hybrid nanocomposite materials are found to be highly active electrocatalysts for OER at lower overpotentials. The nanonet and microsphere-like NiCo₂O₄/rGO catalysts require overpotentials of 0.450 and 0.530 V at a current density of 10 mA cm^?2, and their corresponding Tafel slopes are 53 and 62 mV dec^?1, which are much lower than values reported for non-precious electrocatalysts. Further, both NiCo₂O₄/rGO catalysts show good catalytic stability with current retention more than 92 % over long period of 15,000 s determined by chronoampirometry and at the end of 1000th cycle determined by linear sweep voltammetry. The enhanced OER activity of nanostructured NiCo₂O₄/rGO hybrid catalysts is attributed to synergistic interaction between rGO and NiCo₂O₄, which seems to be essential for maintaining the large contact area at the electrode-electrolyte interface, better mass, and charge transport and to minimize the aggregation of NiCo₂O₄ nanoparticles.     

Ruthenium-modified porous NiCo2O4 nanosheets boost overall water splitting in alkaline solution

Exploring efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) electrocatalysts is crucial for developing water splitting devices. The composition and structure of catalysts are of great importance for catalytic performance. In this work, a heterogeneous Ru modified strategy is engineered to improve the catalytic performance of porous NiCo₂O₄ nanosheets (NSs). Profiting from favorable elements composition and optimized structure property of decreased charge transfer barrier, more accessible active sites and increased oxygen vacancy concentration, the Ru-NiCo₂O₄ NSs exhibits excellent OER activity with a low overpotential of 230 mV to reach the current density of 10 mA/cm² and decent durability. Furthermore, Ru-NiCo₂O₄ NSs show superior HER activity than the pristine NiCo₂O₄ NSs, as well. When assembling Ru-NiCo₂O₄ NSs couple as an alkaline water electrolyzer, a cell voltage of 1.60 V can deliver the current density of 10 mA/cm². This work provides feasible guidance for improving the catalytic performance of spinel-based oxides.     

Facilely Tuning Porous NiCo2O4 Nanosheets with Metal Valence‐State Alteration and Abundant Oxygen Vacancies as Robust Electrocatalysts Towards Water Splitting

Great efforts in developing clean electrochemical water splitting technology leads to the rational design and synthesis of highly efficient oxygen evolution reaction (OER) catalysts with low overpotential and fast reaction kinetics. Herein, we focus on the role that morphology and composition play in the OER performance to rationally design freestanding 3D porous NiCo₂O₄ nanosheets with metal valence states alteration and abundant oxygen vacancies as robust electrocatalysts towards water splitting. Besides metal valence‐state alteration, surface modification regarding the evolution of oxygen vacancies is facilely realized upon the sodium borohydride treatment, which is beneficial for the enhanced OER performance. Taking advantage of the porous nanostructures and abundant surface activity sites with high reactivity, the resultant nanostructures exhibit excellent OER activity and stability in alkaline electrolytes that outperform that of pristine NiCo₂O₄ and commercial RuO₂, thus holding great potential for the water splitting.     

A novel composite electrode for oxygen evolution reaction

FeOOH nanowires were prepared and characterized with X-ray diffraction spectroscopy and scanning electron microscopy. A composite electrode consisting of FeOOH and Ni foam (FeOOH/Ni-foam) was fabricated, and its catalytic performance for oxygen evolution reaction (OER) was evaluated and compared with nanowire NiCo₂O₄/Ni-foam electrode. The mass current density of OER on FeOOH/Ni-foam is around three times of that on NiCo₂O₄/Ni-foam. Ni foam played a key role for the high activity of the FeOOH/Ni-foam. A synergistic mechanism of FeOOH and Ni was proposed to account for the superior catalytic performance of the FeOOH/Ni-foam electrode. Considering the low cost, abundant resource and environment-benign property of FeOOH, the FeOOH/Ni-foam electrode would be a promising anode for OER.     

Hierarchical NiCo2O4 Hollow Microcuboids as Bifunctional Electrocatalysts for Overall Water‐Splitting

Bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline electrolyte may improve the efficiency of overall water splitting. Nickel cobaltite (NiCo₂O₄) has been considered a promising electrode material for the OER. However, NiCo₂O₄ that can be used as an electrocatalyst in HER has not been studied yet. Herein, we report self‐assembled hierarchical NiCo₂O₄ hollow microcuboids for overall water splitting including both the HER and OER reactions. The NiCo₂O₄ electrode shows excellent activity toward overall water splitting, with 10 mA cm^?2 water‐splitting current reached by applying just 1.65 V and 20 mA cm^?2 by applying just 1.74 V across the two electrodes. The synthesis of NiCo₂O₄ microflowers confirms the importance of structural features for high‐performance overall water splitting.     

脊椎状NiCo2O4纳米棒的制备及其析氧和氧还原性能研究

以水热法并进一步焙烧合成脊椎状NiCo₂O₄纳米棒,通过透射电子显微镜（TEM）、X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）和热重分析仪（TG）等来表征其结构形态及热稳定性.采用线性扫描法（LSV）、循环伏安（CV）研究所制备催化剂的在玻碳和旋转圆盘电极上的电催化活性：在0.1 mol·L^-1 KOH溶液中的电催化析氧反应（OER）和电催化氧还原反应（ORR）.研究结果表明,所制备的脊椎状NiCo₂O₄纳米棒有大量的不饱和态,200℃焙烧制备的脊椎状NiCo₂O₄纳米棒析氧过电位最小可达309 mV,Tafel斜率145.6 mV/dec,其氧还原极限电流密度在1600 rmp可达到5.095 mA·cm^-2,电子转移数在3.2~3.8之间,接近四电子转移机理,其优良电化学性能可能是由于暴露了更多的边缘缺陷的缘故.     

Ni/NiCo2O4电极的制备及其析氧反应性能

采用溶胶-凝胶法制备NiCo₂O₄尖晶石粉体, 然后以多孔Ni 为基体, 通过复合溶胶涂覆结合烧结制备Ni/NiCo₂O₄ 涂层电极. 运用扫描电子显微镜(SEM)、能量色散谱(EDS)和X 射线衍射(XRD)表征粉体以及Ni/NiCo₂O₄涂层电极的组成和结构. 采用循环伏安(CV), 稳态极化(LSV), 电化学阻抗谱(EIS), 恒电位阶跃以及恒电位长时间电解研究涂层电极在5 mol·L^-1 KOH溶液中的电催化析氧反应(OER). 结果表明: Ni/NiCo₂O₄涂层电极与多孔Ni 电极对比, 具有低的析氧过电位、高的比表面积和高的稳定性能; 其中比表面积增大了28.69倍,表观活化能在不同过电位分别降低了166.78和162.15 kJ·mol^-1.     

Hierarchical NiCo2O4 nanorods as an efficient cathode catalyst for rechargeable non-aqueous Li–O2 batteries

NiCo₂O₄ nanorods were synthesized by a hydrothermal method followed by low temperature calcination. FESEM and TEM analyses confirmed that the as-prepared materials consist of a hierarchical nanorod structure. When applied as cathode catalysts in rechargeable Li–O₂ batteries, NiCo₂O₄ nanorods exhibited a superior catalytic activity, including low charge over-potential, high discharge capacity and high-rate capability.     

Ultrathin Spinel‐Structured Nanosheets Rich in Oxygen Deficiencies for Enhanced Electrocatalytic Water Oxidation

Electrochemical water splitting is a clean technology for H₂ fuels, but greatly hindered by the slow kinetics of the oxygen evolution reaction (OER). Herein, a series of spinel‐structured nanosheets with oxygen deficiencies and ultrathin thicknesses were designed to increase the reactivity and the number of active sites of the catalysts, which were then taken as an excellent platform for promoting the water oxidation process. Theoretical investigations showed that the oxygen vacancies confined in the ultrathin nanosheet could lower the adsorption energy of H₂O, leading to increased OER efficiency. As expected, the NiCo₂O₄ ultrathin nanosheets rich in oxygen vacancies exhibited a large current density of 285 mA cm^?2 at 0.8 V and a small overpotential of 0.32 V, both of which are superior to the corresponding values of bulk samples or samples with few oxygen deficiencies and even higher than those of most reported non‐precious‐metal catalysts. This work should provide a new pathway for the design of advanced OER catalysts.     

Flower-like NiCo2S4/NiFeP/NF composite material as an effective electrocatalyst with high overall water splitting performance

Rational design and building of high efficiency, secure and inexpensive electrocatalyst is a pressing demand and performance to promote sustainable improvement of hydrogen energy. The bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution response (HER) with high catalytic performance and steadiness in the equal electrolyte are extra treasured and meaningful. Herein, a unique three-dimensional (3D) structure electrocatalyst for NiCo₂S₄ growing on the flower-like NiFeP was designed and synthesized in this study. The results show that the flower-like NiCo₂S₄/NiFeP/NF composite electrocatalyst has large specific surface area, appropriate electrical conductivity, and greater lively websites uncovered in the three-dimensional structure, and affords extraordinary electrocatalytic overall performance for the ordinary water splitting. In alkaline solution, the OER and HER overpotentials of NiCo₂S₄/NiFeP/NF only need 293 mV and 205 mV overpotential to provide the current densities of 100 mA/cm² and 50 mA/cm², respectively. This high electrocatalytic activity exceeds the catalytic activity of most nickel-iron based electrocatalysts for OER and HER process. Accordingly, the optimized NiCo₂S₄/NiFeP/NF sample has higher stability (24 h) at 1.560 and 10 mA/cm², which extensively speeds up the overall water splitting process. In view of the above performance, this work offers a fine approach for the further improvement of low fee and excessive effectivity electrocatalyst.     

The gas phase reaction between CO2 and lanthanide atoms. A test of a model for the isokinetic effect

Summary Co₃O₄, NiCo₂O₄ and LaCo₂O₄catalysts were synthesizedby the citric acid-ligated method. These catalysts containing Co-oxide active components can largely lower the temperature of soot combustion under tight contact conditions. Under the conditions of loose contact NiCo₂O₄ cannot promote soot combustion, but LaCo₂O₄ can effectively promote soot combustion because the nanometric perovskite-type catalyst LaCoO₃produced in the LaCo₂O₄sample.</o:p>     

Low charge overpotentials and extended full cycling capability in lithium-oxygen batteries by controlling the nature of discharge products

Hollow NiCo₂O₄ microspheres with a highly hierarchical porous structure were synthesized and conducted as catalysts for lithium-oxygen batteries. The influence of NiCo₂O₄ on the discharge products was investigated. The NiCo₂O₄ showed the capability to promote the formation of lithium deficient Li_2 − xO₂ and exerted a significant influence on the electrochemical performance of lithium-oxygen batteries with a low charge overpotential and extended full cycling over 50 cycles.     

A Dissolution/Precipitation Equilibrium on the Surface of Iridium‐Based Perovskites Controls Their Activity as Oxygen Evolution Reaction Catalysts in Acidic Media

Recently, Ir^V‐based perovskite‐like materials were proposed as oxygen evolution reaction (OER) catalysts in acidic media with promising performance. However, iridium dissolution and surface reconstruction were observed, questioning the real active sites on the surface of these catalysts. In this work, Sr₂MIr^(V)O₆ (M=Fe, Co) and Sr₂Fe_0.5Ir_0.5^(V)O₄ were explored as OER catalysts in acidic media. Their activities were observed to be roughly equal to those previously reported for La₂LiIrO₆ or Ba₂PrIrO₆. Coupling electrochemical measurements with iridium dissolution studies under chemical or electrochemical conditions, we show that the deposition of an IrO_x layer on the surface of these perovskites is responsible for their OER activity. Furthermore, we experimentally reconstruct the iridium Pourbaix diagram, which will help guide future research in controlling the dissolution/precipitation equilibrium of iridium species for the design of better Ir‐based OER catalysts.     

Carbon Dots Integrated NiCo2O4 Hierarchical Nanoneedle Arrays Supported on Ni Foam as Efficient and Stable Electrode for Hydrogen and Oxygen Evolution Reactions

The production of hydrogen and oxygen via water electrolysis has become a sustainable and encouraging pathway for the establishment of new energy sources. Herein, we report the successful growth of hierarchical NiCo₂O₄‐carbon dots (CDs) nanoneedle arrays supported on nickel foam through a simple and environmentally benign hydrothermal self‐assembly technique. The designed material acts as a binder free electrode and shows bifunctional electrocatalytic activity for both hydrogen evolution reaction (HER) as well as oxygen evolution reaction (OER) in alkaline medium. An electrocatalyst sample with an optimal loading of CDs (25 mg) requires a low overpotential of 146 mV to achieve a current density of 10 mA/cm² for the HER in an alkaline medium, whereas it requires an overpotential of 390 mV to achieve a current density of 50 mA/cm² for the OER in the same alkaline medium. The excellent electrocatalytic activities of the sample with loading of CD can be ascribed due to the presence of large number of exposed active sites offered by CD/NiCo₂O₄ and the enhanced electron transfer processes occurring as a result of hierarchical structure composed of three‐dimensional nickel foam and the NiCo₂O₄?CDs nanoneedle arrays. Thus, the synthesis method introduced in this present work is a facile and cost‐effective approach for the construction of bifunctional electrocatalysts with high reactivity and excellent durability.     

ACo_2O_4/HZSM-5催化剂上N_2O的直接分解

分别采用柠檬酸络合燃烧法和低温络合浸渍法制备尖晶石型复合金属氧化物催化剂ACo2O4(A=Mg,Ni,Zn)和分子筛负载尖晶石型复合金属氧化物催化剂ACo2O4/HZSM-5(A=Mg,Fe,Ni,Cu,Zn,Zr,La).采用X射线衍射(XRD)、氨程序升温脱附(NH3-TPD)、扫描电子显微镜(SEM)和X射线能谱(EDS)等手段对催化剂进行表征,并在固定床微型反应器中评价其催化分解N2O活性.实验结果表明,A位离子种类影响ACo2O4/HZSM-5催化剂活性,以Ni、Fe、Zr或La为A位离子时,催化剂的活性较好,N2O分解温度低.ACo2O4/HZSM-5催化剂的活性高于ACo2O4尖晶石型复合氧化物,一方面是ACo2O4在分子筛HZSM-5载体上高度分散,使其以超细颗粒形态存在,另一方面ACo2O4/HZSM-5催化剂具有适宜的酸性,可提高催化剂的活性.     

Active Electron Density Modulation of Co3O4‐Based Catalysts Enhances their Oxygen Evolution Performance

Despite the fact that many strategies have been developed to improve the efficiency of the oxygen evolution reaction (OER), the precise modulation of the surface electronic properties of catalysts to improve their catalytic activity is still challenging. Herein, we demonstrate that the surface active electron density of Co₃O₄ can be effectively regulated by an argon‐ion irradiation method. X‐ray photoelectron and synchrotron x‐ray absorption spectroscopy, UV photoelectron spectrometry, and DFT calculations show that the surface active electron density band center of Co₃O₄ has been upshifted, leading to a significantly enhanced absorption capability of the oxo group. The optimized Co₃O₄‐based catalysts exhibit an excellent overpotential of 260 mV at 10 mA cm^?2 and Tafel slope of 54 mV dec^?1, superior to the capability of the benchmark RuO₂, representing one of the best Co‐based OER catalysts. This approach could guide the future rational design and discovery of ideal electrocatalysts.     

Active Electron Density Modulation of Co3O4-Based Catalysts Enhances their Oxygen Evolution Performance

Despite the fact that many strategies have been developed to improve the efficiency of the oxygen evolution reaction (OER), the precise modulation of the surface electronic properties of catalysts to improve their catalytic activity is still challenging. Herein, we demonstrate that the surface active electron density of Co₃O₄ can be effectively regulated by an argon-ion irradiation method. X-ray photoelectron and synchrotron x-ray absorption spectroscopy, UV photoelectron spectrometry, and DFT calculations show that the surface active electron density band center of Co₃O₄ has been upshifted, leading to a significantly enhanced absorption capability of the oxo group. The optimized Co₃O₄-based catalysts exhibit an excellent overpotential of 260 mV at 10 mA cm⁻² and Tafel slope of 54 mV dec⁻¹, superior to the capability of the benchmark RuO₂, representing one of the best Co-based OER catalysts. This approach could guide the future rational design and discovery of ideal electrocatalysts.     

Facile synthesis of NiCo2O4 nanorods for electrocatalytic oxidation of methanol

Fuel cell performance largely relies on the activity of catalyst; hence development of high performance electrocatalysts for the electrooxidation of methanol is highly essential for the further development in fuel cell technology. Herein, we demonstrate a facile hydrothermal approach for the growth of NiCo₂O₄ nanorods and their application in the methanol electrooxidation. The morphology and surface area investigation reveal the growth of NiCo₂O₄ nanorods with an average length of 500 nm and a specific surface area of 123 m²/g, respectively. The NiCo₂O₄ nanorods displayed a larger electrochemical activity towards the electrooxidation of methanol in alkaline pH than the quasi-spherical NiCo₂O₄ nanoparticles. On the NiCo₂O₄ nanorod based electrode a higher catalytic current density of 129 mA/cm² and a high stability with 86% current retention was achieved, signifying that the current non-Pt based catalyst could be a non-expensive alternative candidate for high performance fuel cell application.     

g-C3N4/双钙钛矿复合材料的制备及氧催化性能

通过溶胶-凝胶法制备出不同Ni掺杂比例的双钙钛矿Sr_2Ni_xCo_(2-x)O_6(x=0.2,0.4,0.6,0.8),通过热分解法制备出具有层状结构的纳米颗粒g-C_3N_4,并制备其复合物催化剂。将双钙钛矿和g-C_3N_4分别制备成双功能电极片,用于测试其对氧还原(ORR)和氧析出(OER)的催化活性,然后选取具有最佳氧催化活性的Ni掺杂比例x=0.4的双钙钛矿与一定重量比例的g-C_3N_4进行复合,测试复合催化剂的氧催化活性。结果表明,复合后的催化剂催化效果明显优于单一催化剂,当g-C_3N_4添加量占双钙钛矿的30%(w/w)时复合催化剂催化氧还原反应的最大电流密度为395.7 mA·cm~(-2)(-0.6 V vs Hg/HgO),氧析出反应的最大电流密度为372.0mA·cm~(-2)(1 V vs Hg/HgO),这表明g-C_3N_4与Sr_2Ni_(0.4)Co_(1.6)O_6复合后协同催化能够提高双钙钛矿的氧催化活性。     

A Permselective CeOx Coating To Improve the Stability of Oxygen Evolution Electrocatalysts

Highly active NiFeO_x electrocatalysts for the oxygen evolution reaction (OER) suffer gradual deactivation with time owing to the loss of Fe species from the active sites into solution during catalysis. The anodic deposition of a CeO_x layer prevents the loss of such Fe species from the OER catalysts, achieving a highly stable performance. The CeO_x layer does not affect the OER activity of the catalyst underneath but exhibits unique permselectivity, allowing the permeation of OH^? and O₂ through while preventing the diffusion of redox ions through the layer to function as a selective O₂‐evolving electrode. The use of such a permselective protective layer provides a new strategy for improving the durability of electrocatalysts.