characterization and analysis of &#945;-ni(oh)2 nanosheets

氢氧化镍纳米片的微波合成与表征

Nickel hydroxide, Ni(OH)2, is used for numerous applications including nickel-zinc and nickel-metal hydride batteries1,2,3,4, fuel cells4, water electrolyzers4,5,6,7,8,9, supercapacitors4, photocatalysts4, anion exchangers10, and many other analytical, electrochemical, and sensor applications4,5. Ni(OH)2 has two predominant crystal structures: &#946;-Ni(OH)2 and &#945;-Ni(OH)211. &#946;-Ni(OH)2 adopts a brucite-type Mg(OH)2 crystal structure, while &#945;-Ni(OH)2 is a turbostratically layered form of &#946;-Ni(OH)2 intercalated with residual anions and water molecules from the chemical synthesis4. Within &#945;-Ni(OH)2, the intercalated molecules are not within fixed crystallographic positions but have a degree of orientational freedom, and also function as an interlayer glue stabilizing the Ni(OH)2 layers4,12. The interlayer anions of &#945;-Ni(OH)2 affect the average Ni oxidation state13 and influence the electrochemical performance of &#945;-Ni(OH)2 (relative to &#946;-Ni(OH)2) toward battery2,13,14,15, capacitor16, and water-electrolysis applications17,18.
Ni(OH)2 can be synthesized by chemical precipitation, electrochemical precipitation, sol-gel synthesis, or hydrothermal/solvothermal synthesis4. Chemical precipitation and hydrothermal synthesis routes are widely utilized in the production of Ni(OH)2, and different synthetic conditions alter the morphology, crystal structure, and electrochemical performance. The chemical precipitation of Ni(OH)2 involves adding a highly basic solution to an aqueous nickel (II) salt solution. The phase and crystallinity of the precipitate are determined by the temperature and&#160;identities&#160;and concentrations of the nickel (II) salt and&#160;basic solution used4.
Hydrothermal synthesis of Ni(OH)2 involves heating an aqueous solution of precursor nickel (II) salt in a pressurized reaction vial, allowing the reaction to proceed at higher temperatures than ordinarily allowed under ambient pressure4. Hydrothermal reaction conditions typically favor &#946;-Ni(OH)2, but &#945;-Ni(OH)2 can be synthesized by (i) using an intercalation agent, (ii) using a non-aqueous solution (solvothermal synthesis), (iii) lowering the reaction temperature, or (iv) including urea in the reaction, resulting in ammonia-intercalated &#945;-Ni(OH)24. The hydrothermal synthesis of Ni(OH)2 from nickel salts occurs via a two-step process that involves a hydrolysis reaction (equation 1) followed by an olation condensation reaction (equation 2).19
[Ni(H2O)N]2+ + hH2O &#8596; [Ni(OH)h(H2O) N-h](2-h)++ hH3O+ (1)
Ni-OH + Ni-OH2 Ni-OH-Ni + H2O (2)
Microwave chemistry has been used for the one-pot synthesis of a wide variety of nanostructured materials and is based on the ability of a specific molecule or material to convert microwave energy into heat20. In conventional hydrothermal reactions, the reaction is initiated by the direct absorption of heat through the reactor. In contrast, within microwave-assisted hydrothermal reactions, the heating mechanisms are dipolar polarization of the solvent oscillating in a microwave field and ionic conduction generating localized molecular friction20. Microwave chemistry can increase the reaction kinetics, selectivity, and yield of chemical reactions20, making it of significant interest for a scalable, industrially viable method to synthesize Ni(OH)2.
For alkaline battery cathodes, the &#945;-Ni(OH)2 phase provides improved electrochemical capacity compared with the &#946;-Ni(OH)2 phase13, and synthetic methods to synthesize &#945;-Ni(OH)2 are of particular interest. &#945;-Ni(OH)2 has been synthesized by a variety of microwave-assisted methods, which include microwave-assisted reflux21,22, microwave-assisted hydrothermal techniques23,24, and microwave-assisted base-catalyzed precipitation25. The inclusion of urea within the reaction solution significantly influences the reaction yield26, mechanism26,27, morphology, and crystal structure27. The microwave-assisted decomposition of urea was determined to be a critical component for obtaining &#945;-Ni(OH)227. Water content in an ethylene glycol-water solution has been shown to impact the morphology of microwave-assisted synthesis of &#945;-Ni(OH)2 nanosheets24. The reaction yield of &#945;-Ni(OH)2, when synthesized by a microwave-assisted hydrothermal route using an aqueous nickel nitrate and urea solution, was found to depend on the solution pH26. A prior study of microwave synthesized &#945;-Ni(OH)2 nanoflowers using a precursor solution of EtOH/H2O, nickel nitrate, and urea found that temperature (in the range of 80-120 &#176;C) was not a critical factor, provided the reaction is conducted above the urea hydrolysis temperature (60 &#176;C)27. A recent paper that studied the microwave synthesis of Ni(OH)2 using a precursor solution of nickel acetate tetrahydrate, urea, and water found that at a temperature of 150 &#176;C, the material contained both &#945;-Ni(OH)2 and &#946;-Ni(OH)2 phases, which indicates that temperature can be a critical parameter in the synthesis of Ni(OH)228.
Microwave-assisted hydrothermal synthesis can be used to produce high-surface area &#945;-Ni(OH)2 and &#945;-Co(OH)2 by using a precursor solution composed of metal nitrates and urea dissolved in an ethylene glycol/H2O solution12,29,30,31. Metal-substituted &#945;-Ni(OH)2 cathode materials for alkaline Ni-Zn batteries were synthesized using a scaled-up synthesis designed for a large-format microwave reactor12. Microwave-synthesized &#945;-Ni(OH)2 was also used as a precursor for obtaining &#946;-Ni(OH)2 nanosheets12, nickel-iridium nanoframes for oxygen evolution reaction (OER) electrocatalysts29, and bifunctional oxygen electrocatalysts for fuel cells and water electrolyzers30. This microwave reaction route has also been modified to synthesize Co(OH)2 as a precursor for cobalt-iridium nanoframes for acidic OER electrocatalysts31 and bifunctional electrocatalysts30. Microwave-assisted synthesis was also used to produce Fe-substituted &#945;-Ni(OH)2 nanosheets, and the Fe substitution ratio alters the structure and magnetization32. However, a step-by-step procedure for microwave synthesis of &#945;-Ni(OH)2 and the evaluation of how varying reaction time and temperature within a water-ethylene glycol solution affects the crystalline structure, surface area, and porosity, and local environment of interlayer anions within the material&#160;has not been previously reported.
This protocol establishes procedures for high-throughput microwave synthesis of &#945;-Ni(OH)2 nanosheets using a rapid and scalable technique. The effect of reaction temperature and time were varied and evaluated using in situ reaction monitoring, scanning electron microscopy, energy dispersive X-ray spectroscopy, nitrogen porosimetry, powder X-ray diffraction (XRD), and Fourier transform infrared spectroscopy to understand the effects of synthetic variables on reaction yield, morphology, crystal structure, pore size, and local coordination environment of &#945;-Ni(OH)2 nanosheets.

作者聚焦：氢氧化镍纳米片的快速微波辅助水热合成 

微波合成条件对氢氧化镍纳米片结构的影响

Watch this Scientific Journal Video about Characterization and Analysis of α-NiOH2 Nanosheets at JoVE.com

Characterization and Analysis of &amp;#945;-Ni(OH)2 Nanosheets  

α-Ni（OH）2 纳米片的表征与分析

为了通过SEM和EDS表征微波合成的氢氧化镍纳米片的形态和组成，使用水浴超声仪将少量氢氧化镍粉末悬浮在一毫升乙醇中来制备样品。然后将氢氧化镍和乙醇混合物滴铸在SEM存根上，并在收集SEM显微照片和EDS光谱之前，通过在70摄氏度的样品箱中加热存根来蒸发乙醇。为了确定纳米片的表面积和孔隙率，在样品管中加入25毫克氢氧化镍纳米片。在120摄氏度的真空下进行预分析脱气和干燥程序16小时。最后，将样品管从脱气口转移到分析口以收集氮气等温线。对于使用 X 射线衍射或 XRD 进行结构分析，请用氢氧化镍填充零背景粉末 XRD 支架的样品孔。使用铜K-α辐射源在2至80度的2-theta之间以0.01步长的增量收集粉末X射线衍射图。将衰减的总反射率或 ATR 附件配备到傅里叶变换红外或 FTIR 光谱仪上。在两个载玻片之间按压少量氢氧化镍粉末以产生颗粒。然后将氢氧化镍颗粒放在硅ATR晶体上，获得404， 000倒数厘米之间的FTIR光谱，平均16次单独扫描，分辨率为4倒数厘米。扫描电镜显示，微波合成的氢氧化镍是由随机交织的超薄纳米片聚集体组成的。然而，将反应温度从120摄氏度提高到180摄氏度会增加聚集体中单个纳米片的横向片尺寸。此外，在120摄氏度下将反应时间从13分钟增加到30分钟，将有核聚集体的尺寸从约3微米增加到5微米。EDS显示镍、氧、碳和氮在所有合成的纳米片中均匀分布。纳米片的BET表面积为每克61至85平方米，平均孔径为21至35埃，累积体积为每克0.4至0.6立方厘米。所有3个微波合成样品的XRD图谱均显示出α氢氧化镍的特征峰。然而，反应时间和温度会影响峰，如001平面的移动所证明的那样。微波合成纳米片的ATR-FTIR光谱显示出特征性的氧化镍晶格模式。来自配体和结构分子的模式，氰酸盐带和α氢氧化物晶格模式。将反应温度从 120 摄氏度提高到 180 摄氏度改变了氰酸盐、硝酸盐、羟基和水振动模式的频率和相对强度。

characterization-and-analysis-of-nioh2-nanosheets

Research

JoVE Journal

Chemistry

Characterization and Analysis of &#945;-Ni(OH)2 Nanosheets

372 次观看.  Texas State University. 为了通过SEM和EDS表征微波合成的氢氧化镍纳米片的形态和组成，使用水浴超声仪将少量氢氧化镍粉末悬浮在一毫升乙醇中来制备样品。然后将氢氧化镍和乙醇混合物滴铸在SEM存根上，并在收集SEM显微照片和EDS光谱之前，通过在70摄氏度的样品箱中加热存根来蒸发乙醇。为了确定纳米片的表面积和孔隙率，在样品管中加入25毫克氢氧化镍纳米片。在120摄氏度的真空下进行预...

视频: Characterization and Analysis of &#945;-Ni(OH)2 Nanosheets  

Effect of Microwave Synthesis Conditions on the Structure of Nickel Hydroxide Nanosheets

A protocol for rapid, microwave-assisted hydrothermal synthesis of nickel hydroxide nanosheets under mildly acidic conditions is presented, and the effect of reaction temperature and time on the material&#39;s structure is examined. All reaction conditions studied result in aggregates of layered &#945;-Ni(OH)2 nanosheets. The reaction temperature and time strongly influence the structure of the material and product yield. Synthesizing &#945;-Ni(OH)2 at higher temperatures increases the reaction yield, lowers the interlayer spacing, increases crystalline domain size, shifts the frequencies of interlayer anion vibrational modes, and lowers the pore diameter. Longer reaction times increase reaction yields and result in similar crystalline domain sizes. Monitoring the reaction pressure in situ shows that higher pressures are obtained at higher reaction temperatures. This microwave-assisted synthesis route provides a rapid, high-throughput, scalable process that can be applied to the synthesis and production of a variety of transition metal hydroxides used for numerous energy storage, catalysis, sensor, and other applications.

Nickel hydroxide nanosheets are synthesized by a microwave-assisted hydrothermal reaction. This protocol demonstrates that the reaction temperature and time used for microwave synthesis affects the reaction yield, crystal structure, and local coordination environment.

A protocol for rapid, microwave-assisted hydrothermal synthesis of nickel hydroxide nanosheets under mildly acidic conditions is presented, and the effect ...

科研

化学

Microwave-Assisted Synthesis of &#945;-Ni(OH)2 Nanosheets

Microwave-Assisted Synthesis of &amp;#945;-Ni(OH)2 Nanosheets  

Begin preparing the precursor solution by mixing 105 milliliters of ethylene glycol and 15 milliliters of ultrapure water. Then add 4.1 grams of uria and add 5.0 grams of nickel nitrate hexahydrate, and cover the solution. Sonicate the precursor solution for 30 minutes in a bath sonicator filled with ice and water at 40 kilohertz frequency and full power without pulse.Transfer 20 milliliters of the sonic precursor solution into a microwave reaction vial fitted with a PTFE stir bar. Seal the reaction vessel using a locking lid with a PTFE liner. Place the vial inside the microwave reactor and set the reactor program to as fast as possible, which applies maximum power until the desired temperature is achieved.Thereafter, apply variable power to maintain the reaction temperature for 13 to 30 minutes. Upon completion of the reaction, vent the reaction chamber with compressed air until the solution temperature reaches 55 degrees Celsius. Transfer the post reaction solution to 50 milliliter centrifuge tubes.Centrifuge the tubes at room temperature for four minutes, and decant the supernatant. Resuspend the resulting nickel hydroxide nano sheets in 25 milliliters of ultrapure water and centrifuge once more as demonstrated previously. After decanting the supernatant, cover the centrifuge tubes with a tissue or paper towel serving as a porous cover to minimize potential contamination.Finally, dry the nano sheets under an ambient atmosphere in a sample oven at 70 degrees Celsius for 21 hours. At 120 degrees Celsius, the maximum reaction pressure generated was nine to 11.5 pounds per square inch or PSI. Whereas at 180 degrees Celsius, it increased to 138 PSI.Increasing the reaction temperature from 120 to 180 degrees Celsius also changed the post-reaction supernatant color from green to blue. In C2 photographs of the reaction at 180 degrees Celsius showed a murky green color when the reaction terminated, but it changed to murky blue as the reaction cooled. After centrifugation, washing, and drying, all the reactions, irrespective of time and temperature, produced a green powder.The pH of the supernatant of the 180 degree Celsius reaction was much higher relative to the 120 degree Celsius reaction supernatants. The 180 degree Celsius reaction also recorded a much higher yield than the reactions at 120 degrees Celsius.

微波辅助合成α-Ni（OH）2 纳米片

To characterize the morphology and composition of the microwave synthesized nickel hydroxide nanosheets by SEM and EDS, prepare the sample by suspending a small amount of nickel hydroxide powder in one milliliter of ethanol using a water bath sonicator. Then drop cast the nickel hydroxide and ethanol mixture on an SEM stub and evaporate the ethanol by heating the stub in a sample oven at 70 degrees Celsius before collecting the SEM micrographs and EDS spectra. In order to determine the surface area and porosity of the nanosheets, add 25 milligrams of nickel hydroxide nanosheets into the sample tube.Carry out a pre-analysis degassing and drying procedure under vacuum at 120 degrees Celsius for 16 hours. Lastly, transfer the sample tube from the degassing port to the analysis port to collect nitrogen isotherms. For structural analysis using X-ray diffraction or XRD, fill the sample well of a zero-background powder XRD holder with nickel hydroxide.Collect powder X-ray diffractograms using a copper K-alpha radiation source between a 2-theta of 2 to 80 degrees with a 0.01 step increment. Equip the attenuated total reflectance or ATR attachment to the Fourier Transform Infrared or FTIR spectrometer. Press a small amount of nickel hydroxide powder between two glass slides to create a pellet.Then place the nickel hydroxide pellet on the silicon ATR crystal and obtain an FTIR spectrum between 404, 000 reciprocal centimeters as an average of 16 individual scans with a resolution of four reciprocal centimeters. SEM revealed that the microwave synthesized nickel hydroxide was composed of randomly interwoven ultra thin nanosheet aggregates. However, increasing the reaction temperature from 120 to 180 degrees Celsius increased the lateral sheet dimensions of individual nanosheets in the aggregates.Also, increasing the reaction time from 13 to 30 minutes at 120 degrees Celsius increased the nucleated aggregate sizes from about three to five microns. EDS showed a uniform distribution of nickel, oxygen, carbon, and nitrogen within all the synthesized nanosheets. The nanosheets had BET surface areas ranging from 61 to 85 square meters per gram, average pore diameter of 21 to 35 angstroms, and cumulative poor volumes of 0.4 to 0.6 cubic centimeters per gram.The XRD patterns of all three microwave synthesized samples showed characteristic peaks of alpha nickel hydroxide. However, reaction time and temperature affected the peaks as demonstrated by the shifting of the 001 plane. The ATR-FTIR spectra of the microwave synthesized nanosheets showed characteristic nickel oxide lattice mode.Modes from the ligands and structural molecules, cyanate bands and alpha hydroxide lattice modes. Increasing the reaction temperature from 120 to 180 degrees Celsius altered the frequencies and relative intensities of the cyanate, nitrate, hydroxyl, and water vibrational modes.