This work was supported by the Rowland Fellows Program at the Rowland Institute of Harvard University. This work was performed in part at the Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network, which is supported by the National Science Foundation under award no. ECS-0335765. The CNS is part of Harvard University.

1. Preparation of Ni Single Atom Catalyst (NiN-GS)
<ol>
	<li>Preparation of electrospinning precursor solution
	<ol>
		<li>Take a 20 mL scintillation vial, dissolve 0.5 g of polyacrylonitrile (Mw=150,000), 0.5 g of polypyrrolidone (Mw=1,300,000), 0.5 g of Ni(NO3)2&#183;6H2O, and 0.1 g of dicyandiamide (DCDA) in 10 mL of dimethylformamide (DMF).</li>
		<li>Heat the DMF mixture to 80 &#176;C and keep the mixture at 80 &#176;C with constant stirring ...

<ol>
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In the above electrospinning process, two important steps should be noted in material synthesis procedures: 1) heating the DMF mixture (step 1.1.2), and 2) the pump rate adjusting (step 1.2.2) to match the spinning rate. The SEM image in Figure 1A shows the obtained carbon nanofibers interconnected with each other (~200 nm in diameter). They were broken into small pieces by ball milling for characterizations as shown in Figure 1B. Ni nanoparticles were uniformly...

Converting CO2 into chemicals or fuels using clean electricity is becoming increasingly important as a potential route to prevent further CO2 emissions1,2,3,4,5,6. However, this practical application is currently challenged by the low activity and selectivity of CO2 reduction reaction (CO2RR) due to the high kinetic barriers and the competition with hydrogen evolution reaction (HER) in aqueous media. Most of the traditional transition metal catalyst, such as Fe, Co, and Ni, exhibit low CO2RR selectivity due to their superb HER activities7,8. Effectively tuning their material properties to change the reaction pathways on these transition metal catalysts becomes critical to improve their CO2RR selectivity. Among different methods to modify the electronic properties of catalysts, dispersing metal atoms into a single-atom morphology attracts intensive attentions recently due to their dramatically changed catalytic behaviors compared to their bulk counterpart9,10,11. However, due to the high mobility of unbounded atoms, it is quite challenging to obtain single metal atoms without the presence of supportive materials. Therefore, a host matrix material with defects created to confine and coordinate with transition metal atoms is necessary. This could open up new opportunities to: 1) tune the electronic properties of transition metals as CO2RR active sites, and 2) at the same time maintain relatively simple atomic coordination for fundamental mechanism studies. In addition, those transition metal atoms trapped in a confined environment cannot be easily moved around during catalysis, which prevents the nucleation or reconstructions of surface atoms observed in many cases12,13,14.
Two-dimensional layered graphene is of particular interest as host for metal single atoms due to their high electron conductivity, chemical stability, and inertness to both CO2 reduction and HER catalytic reactions. More importantly, Fe, Co, and Ni metals were known to be able to catalyze the carbon graphitization process on their surface15. In short, those transition metals would alloy with carbon during the high temperature thermal annealing process. When the temperature drops, carbon starts to precipitate out of the alloying phase and is catalyzed to form graphene layers on the surface of transition metal. During this process, with graphene defects generated, metal single atoms would be trapped in those graphene defects as the active sites for CO2RR16,17,18,19. Here, we report this detailed protocol intending to help new practitioners in the field of single atom catalysis, as well as to provide an explicit demonstration of on-line CO2 reduction product analysis. More information can be found in our recently published article19 and a series of related works20,21,22,23.

<table border="0" cellpadding="0" cellspacing="0" width="829">
	<tbody>
		<tr height="23">
			<td height="23" style="height:23px;width:216px;">syringe pump&#160;</td>
			<td style="width:164px;">KD Scientific</td>
			<td style="width:151px;">KDS-100</td>
			<td style="width:299px;"></td>
		</tr>
		<tr height="23">
			<td height="23" style="height:23px;width:216px;">tube furnance</td>
			<td style="width:164px;">Lindberg/Blue M</td>
			<td style="width:151px;">TF55035A-1</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">ball miller</td>
			<td style="width:164px;">SPEX SamplePrep</td>
			<td style="width:151px;">5100</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">electrochemical work station</td>
			<td style="width:164px;">BioLogic</td>
			<td style="width:151px;">VMP3</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">pH meter</td>
			<td style="width:164px;">Orion</td>
			<td style="width:151px;">320 PerpHecT&#160;</td>
			<td>2 points calibration before use</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">gas chromatograph</td>
			<td style="width:164px;">Shimadzu</td>
			<td style="width:151px;">GC-2014</td>
			<td>a combined seperation system consisting of molecular sieve 5A, Hayesep Q, Hayesep T, and Hayesep N</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">mass flow controller</td>
			<td>Alicat Scientific&#160;</td>
			<td style="width:151px;">MC-50SCCM-D/5M</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">ultrapure water system</td>
			<td>Millipore</td>
			<td>Synergy</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">vacuum desiccator&#160;</td>
			<td>PolyLab</td>
			<td>55205</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">polyacrylonitrile</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td style="width:151px;">181315</td>
			<td>Mw=150,000</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">polypyrrolidone</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td style="width:151px;">437190</td>
			<td>Mw=1,300,000</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Ni(NO3)26H2O</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td style="width:151px;">244074</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">dicyandiamide</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td style="width:151px;">D76609</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">dimethylformamide</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td style="width:151px;">227056</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">carbon fiber paper&#160;</td>
			<td style="width:164px;">AvCarb</td>
			<td style="width:151px;">MGL370</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Nafion 117 membrane</td>
			<td style="width:164px;">Fuel Cell Store</td>
			<td style="width:151px;">117</td>
			<td>used as proton exchange membrane in H-cell</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">KHCO3</td>
			<td style="width:164px;">Sigma-Aldrich</td>
			<td style="width:151px;">431583</td>
			<td>further purified by electrolysis</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">platinum foil&#160;</td>
			<td style="width:164px;">Beantown Chemical</td>
			<td style="width:151px;">126580</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">saturated calomel electrode</td>
			<td style="width:164px;">CH Instruments</td>
			<td style="width:151px;">CHI150</td>
			<td></td>
		</tr>
		<tr height="27">
			<td height="27" style="height:27px;width:216px;">glassy carbon electrode</td>
			<td style="width:164px;">HTW GmbH</td>
			<td style="width:151px;">SIGRADUR</td>
			<td>1 cm &#215; 2 cm</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">wax</td>
			<td>Apiezon</td>
			<td style="width:151px;">W-W100</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Nafion 117 solution</td>
			<td>Sigma-Aldrich</td>
			<td>70160</td>
			<td>used as ionomer in catalyst ink preparation&#160;</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">forming gas</td>
			<td>Airgas</td>
			<td>UHP</td>
			<td>5% H2 balanced with Ar</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">carbon dioxide</td>
			<td>Airgas</td>
			<td>LaserPlus</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">sandard gas</td>
			<td>Airgas</td>
			<td>customized</td>
			<td>500 ppm CO, 500 ppm CH4, 1000 ppm H2 balanced with Ar</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">sandard gas</td>
			<td>Air Liquide</td>
			<td>customized</td>
			<td>100 ppm H2, 100 ppm CO and other alkanes balanced with Ar</td>
		</tr>
	</tbody>
</table>

synthesis and performance characterizations of transition metal single atom catalyst for electrochemical co2 reduction

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity in aqueous CO2 reduction. Different from traditional metal nanocrystals, the synthesis of metal single atoms involves a matrix material that can confine those single atoms and prevent them from aggregation. We report an electrospinning and thermal annealing method to prepare Ni single atoms dispersed and coordinated in a graphene shell, as active centers for CO2 reduction to CO. During the synthesis, N dopants play a critical role in generating graphene vacancies to trap Ni atoms. Aberration-corrected scanning transmission electron microscopy and three-dimensional atom probe tomography were employed to identify the single Ni atomic sites in graphene vacancies. Detailed setup of electrochemical CO2 reduction apparatus coupled with an on-line gas chromatography is also demonstrated. Compared to metallic Ni, Ni single atom catalyst exhibit dramatically improved CO2 reduction and suppressed H2 evolution side reaction.

Scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDX) mapping images are shown in Figure 1 for the morphology characterization of NiN-GS. Three-dimensional atom probe tomography (3D-APT) results are shown in Figure 2 for the direct identification of single Ni sites distribution as well as their neighboring chemical environment. On-line electrochemical G...

Watch this Scientific Journal Video about Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction at JoVE.com

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Here, we present a protocol for the synthesis and electrochemical testing of transition metal single atoms coordinated in graphene vacancies as active centers for selective carbon dioxide reduction to carbon monoxide in aqueous solutions.

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

This protocol presents both the synthesis method of the Ni single atom catalyst, and the electrochemical testing of its catalytic activity and selectivity ...

The overall goal of this procedure is the preparation in the electrochemical application of Transition Metal Single Atoms coordinated in graphene vacancies towards selective carbon dioxide reduction in aqueous solutions. This method can help answer key questions in the electro-catalytic CO2 reduction field about the preparation of catalysts and the determination of product seal activity. The main advantage of this technique is that single atoms can be trapped in graphene vacancies and the transition metal neno-particles can be tightly surrounded by graphene layers.To begin the procedure, in a 20 milliliter scintillation vial, combine zero point five grams of polyacrylonitrile, zero point five grams of polyvinylpyrrolidone, zero point five grams of Nickel(II)hexahydrate, and zero point one grams of dicdyandiamide, with 10 milliliters of dimethylformamide. Heat the mixture to 80 degrees Celsius and stir until clear and green. Allow the pre-cursor mixture to cool to room temperature afterwards.Then, mount an eight centimeter by eight centimeter piece of zero point three seven millimeter thick carbon fiber paper as the collection substrate in a conventional electro spinning apparatus. Draw five milliliters of the pre-cursor mixture into a five milliliter syringe. Equip the syringe with a 19 gauge, two inch needle, as the spinning tip and mount the syringe on a syringe pump.Configure the apparatus for a 15 centimeter space between the spinning and the collector surface. Connect the positive terminal of a power supply to the needle, and the negative terminal to the collection substrate. Configure the power supply to deliver 15 kilovolts of static voltage tot he spinning tip, and minus four kilovolts against the collection substrate.Run the syringe pump at one point two milliliters per hour and start electro spinning. Once finished, turn off the power and transfer the polymer fiber coated substrate to a piece of aluminum foil. In a box furnace, heat the coated substrate to 300 degrees Celsius over the course of one point five hours.Hold the sample at that temperature for 30 minutes to oxidize the polymer fibers which will detach from the substrate as a stand alone film. Remove the substrate and the detached oxidized polymer nano-fiber film from the furnace. Allow the film to cool to room temperature in air.Then, cut the film into approximately zero point five centimeter by two centimeter pieces and collect the pieces in a quartz boat. Place the boat in a tube furnace in the center of the heating zone. Perch the sample in the furnace atmosphere three times with a gas mixture of five percent hydrogen in argon.Then, maintain the gas flow at 100SCCM and the furnace pressure at one torque. Ramp the furnace first to 300 degrees Celsius over the course of ten minutes. And then to 750 degrees Celsius over the course of two hours.Both at constant wrap rates. Hold the sample at 750 degrees Celsius for one hour. Then, turn off the heat and allow the sample to cool to room temperature in the furnace under the 100SCCM flow of five percent hydrogen and argon.Seal the cooled sample in a six millimeter stainless steel milling ball in a stainless steel milling jar. Ball mill the sample at 3, 000 RPM in 60 hertz for five minutes to obtain the nickel nitrogen graphene shell catalyst as a Nano powder. To begin the measurement procedure, dissolve two point five grams of potassium bicarbonate in 250 milliliters of ultra pure water as the electrolyte.Electrolize the electrolyte solution between two graphite rods at zero point one milliamps for 24 hours to remove trace metal ions. Then, cover the back of a clean, electrochemically polished, one centimeter by two centimeter glassy carbon electrode with an electrochemically inert hydrophobic wax dissolved in toluene. Next, place in a four milliliter scintillation vial, five milligrams of nickel nitrogen graphene shell catalyst nano powder, one milliliter of ethanol, and 100 microliters of a five percent iodymer solution in isopropyl alcohol.Sonicate the mixture for 20 minutes to obtain a homogeneous catalyst ink suspension. Apply 80 microliters of the catalyst ink to the surface of the glassy carbon electrode. Dry the catalyst covered electrode in a vacuum desiccator for five to 10 minutes.Then, equip a gas tight H-type electrochemical cell with a proton exchange membrane. Add a nitrogen gas line to the chamber that will contain the working electrode. Place the catalyst covered working electrode and a saturated calomel reference electrode in one compartment of the cell, and a platinum foil counter electrode in the other.Add about 25 milliliters of the purified electrolyte solution to each compartment. Connect the electrolytes to a multi-channel potentiostat. Bubble nitrogen gas through electrolyte for 30 minutes at 50SCCM to saturate the electrolyte.Then, select cyclic voltammetry in the Potentiostat software. Configure the experiment for five continuous CV scans from minus zero point five volts to minus one point eight volts versus SCE at 50 millivolts per second with a working electrode potential range of minus 10 volts to 10 volts, and an automatic current range. Acquire a CV in the nitrogen saturated electrolyte.Then change the gas line to carbon dioxide and bubble carbon dioxide through the electrolyte at 50SCCM for 30 minutes. Then, while still bubbling carbon dioxide at 50SCCM. Acquire another CV using the same parameters as previously used.Next, select potentiostatic electrochemical impedance spechtrology in the Potentiostat software. Set the frequency range to zero point one hertz to 200 kilohertz. Use the open circuit potential as the initial potential.Perform an impeded scan and record the solution resistant value. Correct the measured potentials for the voltage drop using this information. Assemble an H-type electrochemical cell with a nickel nitrogen graphene shell coated working electrode in purified zero point one molar potassium bicarbonate as the electrolyte, as previously described.Set up a gas chromatograph to use a separation system of five angstrom molecular sieves in a series of columns for separating low molecular weight compounds. Equip the GC with a thermal conductivity detector and a flame ionization detector with a methodizer. Direct the exhaust from the electrochemical cell chamber containing the working electrode to the sample loop of the GC using vinyl tubing with an inner diameter of one 16th of an inch.Run another length of vinyl tubing from the chamber with the counter electrode to a flask of water as a gas flow monitor. Connect the electrodes to a multi-channel potentiostat and saturate the electrolyte with carbon dioxide gas as previously described. Maintain the carbon dioxide flow rate at precisely 50.0SCCM.Use the Potentiostat software to report a chrono and parametric curve. While stepping the of working electrode from minus zero point three volts to minus one point zero volts versus RAG. Holding for 15 minutes at each step.For each potential step after 10 minutes of continuous electrolysis, sample the gas products with the GC using a run time of 16 minutes. Determine the hydrogen monoxide contents in the exhaust from the TCD and FID signals, respectively. Calculate the partial current density and faradaic efficiency for each product.Nickel nano particles were found to be uniformly distributed in the carbon nano fibers of the catalyst. The nano particles were encapsulated in approximately 10 nanometers thick shells of graphene, preventing direct contact between the nickel nano particles and the aqueous slater, and thus suppressing a hydrogen evolution reaction. Energy dispersive x-ray spectroscopy mapping in atom probe tomography showed that nickel atoms were incorporated into the graphene layers around the nano particles.Nickel atoms were also dispersed in carbon in areas further from nickel nano particles. Nickel single atoms were found to be coordinated in graphene vacancies with a small percentage also coordinated with nitrogen atoms. Statistical analysis indicated that most of the nickel in this nickel poor area was in single atom form.The electro-catalytic carbon dioxide reduction reaction performance of the catalyst at various applied potentials was evaluated in real time by a GC connected to the electrochemical cell exhaust. The faradaic efficiencies of carbon monoxide and hydrogen were determined to be approximately 93 percent and 12 percent respectively at minus zero point eight two volts versus RAG. After it's development, this tannic paved the way for researchers in the field of electrolysis to explore these transition metals single atom catalysts in artificial photosynthesis as well as other energy conversion applications.

synthesis-performance-characterizations-transition-metal-single-atom

Research

JoVE Journal

Chemistry

17.8K ビュー.  Harvard University. The overall goal of this procedure is the preparation in the electrochemical application of Transition Metal Single Atoms coordinated in graphene vacancies towards selective carbon dioxide reduction in aqueous solutions. This method can help answer key questions in the electro-catalytic CO2 reduction field about the preparation of catalysts and the determination of product seal activity. The main advantage of this technique is that single atoms can be trapped in graphene vacancies and the tra...

ビデオ: Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction

Here, we present a protocol for the synthesis and electrochemical testing of transition metal single atoms coordinated in graphene vacancies as active centers for selective carbon dioxide reduction to carbon monoxide in aqueous...

synthesis of platinum-nickel nanowires and optimization for oxygen reduction performance

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

&#160; The protocol describes the synthesis and electrochemical testing of platinum-nickel nanowires. Nanowires were synthesized by the galvanic displacement of a nickel nanowire template. Post-synthesis processing, including hydrogen annealing, acid leaching, and oxygen annealing were used to optimize nanowire performance and durability in the oxygen reduction...

reverse microemulsion-mediated synthesis of monometallic and bimetallic early transition metal carbide and nitride nanoparticles

Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles

A &#8220;removable ceramic coating method&#8221; is presented in visual format for the synthesis of non-sintered and metal-terminated monometallic and bimetallic early transition metal carbide and nitride nanoparticles with tunable sizes and crystal...

hkust-1 as a heterogeneous catalyst for the synthesis of vanillin

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

multiscale sampling of a heterogeneous water/metal catalyst interface using density functional theory and force-field molecular dynamics

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

The goal of the protocol presented here is to generate and sample trajectories of configurations of liquid water molecules around catalytic species on a flat transition metal surface. The sampled configurations can be used as starting structures in quantum mechanics-based...

synthesis of single-crystalline core-shell metal-organic frameworks

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Here, we demonstrate a protocol for the two-step synthesis of single-crystalline core-shells using a non-isostructural metal-organic framework (MOF) pair, HKUST-1 and MOF-5, which have well-matched crystal...

metal-assisted electrochemical nanoimprinting of porous and solid silicon wafers

Metal-Assisted Electrochemical Nanoimprinting of Porous and Solid Silicon Wafers

A protocol for metal-assisted chemical imprinting of 3D microscale features with sub-20 nm shape accuracy into solid and porous silicon wafers is...

co2 photoreduction to ch4 performance under concentrating solar light

CO2 Photoreduction to CH4 Performance Under Concentrating Solar Light

We present a protocol for improving the performance of CO2 photoreduction to CH4 by heightening the incident light intensity via concentrating solar energy...

CO2 Photoreduction to CH4 Performance Under Concentrating Solar Light

a microwave-assisted direct heteroarylation of ketones using transition metal catalysis

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

Heteroaryl compounds are important molecules utilized in organic synthesis, medicinal and biological chemistry. A microwave-assisted heteroarylation using palladium catalysis provides a rapid and efficient method to attach heteroaryl moieties directly to ketone...

synthesis of nine-atom deltahedral zintl ions of germanium and their functionalization with organic groups

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

We present the high-temperature synthesis of intermetallic precursors K4Ge9, their dissolution in ethylenediamine to form Ge94- deltahedral Zintl ions, and the reaction of the clusters with alkynes to form organo-Zintl ions.  The latter are characterized by  electrospray mass spectrometry in solutions and by single-crystal X-ray diffraction in the solid...

synthesis and characterization of functionalized metal-organic frameworks

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these...

synthesis and catalytic performance of gold intercalated in the walls of mesoporous silica

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

Here, we present a protocol with a sol-gel process to synthesize gold intercalated in the walls of mesoporous materials (GMS), which is confirmed to possess a mesoporous matrix with gold intercalated in the walls imparting great stability and...

synthesis of metal nanoparticles supported on carbon nanotube with doped co and n atoms and its catalytic applications in hydrogen production

Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production

Here, we present a protocol to synthesize Co nanoparticles supported on carbon nanotubes with Co- and N- dopants for hydrogen...

a method to manipulate surface tension of a liquid metal via surface oxidation and reduction

A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction

We present a method to control the interfacial energy of a liquid metal in an electrolyte via electrochemical deposition (or removal) of a surface oxide layer. This simple method can control the capillary behavior of gallium-based liquid metals by tuning the interfacial energy rapidly, significantly, and reversibly using modest...

a rapid synthesis method for au, pd, and pt aerogels via direct solution-based reduction

A Rapid Synthesis Method for Au, Pd, and Pt Aerogels Via Direct Solution-Based Reduction

A rapid, direct solution-based reduction synthesis method to obtain Au, Pd, and Pt aerogels is...

a direct, regioselective and atom-economical synthesis of 3-aroyl-n-hydroxy-5-nitroindoles by cycloaddition of 4-nitronitrosobenzene with alkynones

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

3-Aroyl-N-hydroxy-5-nitroindoles were synthesized by cycloaddition of 4-nitronitrosobenzene with a conjugated terminal alkynone in a one-step thermal procedure. Preparation of the nitrosoarene and of the alkynones were adequately reported and respectively through oxidation procedures on the corresponding aniline and on the...

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

metal-free synthesis of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and...

experimental approaches for the synthesis of low-valent metal-organic frameworks from multitopic phosphine linkers

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers  

Here, we describe a protocol for the synthesis of low-valent metal-organic frameworks (LVMOFs) from low-valent metals and multitopic phosphine linkers under air-free conditions. The resulting materials have potential applications as heterogeneous catalyst mimics of low-valent metal-based homogeneous...

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers

electrophoretic crystallization of ultrathin high-performance metal-organic framework membranes

Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes

A simple, reproducible, and versatile approach for the synthesis of intergrown, polycrystalline metal-organic framework membranes on a wide range of unmodified porous and non-porous supports is...

in situ ftir spectroscopy as a tool for investigation of gas/solid interaction: water-enhanced co2 adsorption in uio-66 metal-organic framework

In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework

The use of FTIR spectroscopy for investigation of the surface properties of polycrystalline solids is described. Preparation of sample pellets, activation procedures, characterization with probe molecules and model studies of CO2 adsorption are...

In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework

Anticancer Metal Complexes: Synthesis and Cytotoxicity Evaluation by the MTT Assay

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; therefore their preparation should be conducted under an inert atmosphere. Evaluation of the anticancer activity of these complexes can be achieved by the MTT assay.
The MTT assay is a colorimetric viability assay based on enzymatic reduction of the MTT molecule to formazan when it is exposed to viable cells. The outcome of the reduction is a color change of the MTT molecule. Absorbance measurements relative to a control determine the percentage of remaining viable cancer cells following their treatment with varying concentrations of a tested compound, which is translated to the compound anticancer activity and its IC50 values. The MTT assay is widely common in cytotoxicity studies due to its accuracy, rapidity, and relative simplicity.
Herein we present a detailed protocol for the synthesis of air sensitive metal based drugs and cell viability measurements, including preparation of the cell plates, incubation of the compounds with the cells, viability measurements using the MTT assay, and determination of IC50 values.

A method for synthesis of air-sensitive titanium and vanadium anticancer agents is described, along with the evaluation of their cytotoxic activity towards human cancer cell line by the MTT Assay.

Titanium (IV) and vanadium (V) complexes are highly potent anticancer agents. A challenge in their synthesis refers to their hydrolytic instability; ...

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The silica-encapsulated metal oxide nanoparticles are then carburized in a methane/hydrogen atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal carbide nanoparticles. During the carburization process, the silica shells prevent the sintering of adjacent carbide nanoparticles while also preventing the deposition of excess surface carbon. Alternatively, the silica-encapsulated metal oxide nanoparticles can be nitridized in an ammonia atmosphere at temperatures over 800 &#176;C to form silica-encapsulated early transition metal nitride nanoparticles. By adjusting the reverse microemulsion parameters, the thickness of the silica shells, and the carburization/nitridation conditions, the transition metal carbide or nitride nanoparticles can be tuned to various sizes, compositions, and crystal phases. After carburization or nitridation, the silica shells are then removed using either a room-temperature aqueous ammonium bifluoride solution or a 0.1 to 0.5 M NaOH solution at 40-60 &#176;C. While the silica shells are dissolving, a high surface area support, such as carbon black, can be added to these solutions to obtain supported early transition metal carbide or nitride nanoparticles. If no high surface area support is added, then the nanoparticles can be stored as a nanodispersion or centrifuged to obtain a nanopowder.

A &#8220;removable ceramic coating method&#8221; is presented in visual format for the synthesis of non-sintered and metal-terminated monometallic and bimetallic early transition metal carbide and nitride nanoparticles with tunable sizes and crystal structures.

A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The ...

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension.
Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries.
Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude ( &#820;500 mN/m to near zero). Furthermore, this method requires only a very modest potential (&#60; 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests.

We present a method to control the interfacial energy of a liquid metal in an electrolyte via electrochemical deposition (or removal) of a surface oxide layer. This simple method can control the capillary behavior of gallium-based liquid metals by tuning the interfacial energy rapidly, significantly, and reversibly using modest voltages.

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where ...

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately 200 different odorant compounds in addition to vanillin. The natural extraction of vanillin (from the orchid Vanilla planifolia, Vanilla tahitiensis and Vanilla pompon) represents only 1% of the worldwide production and since this process is expensive and very long, the rest of the production of vanillin is synthesized. Many biotechnological approaches can be used for the synthesis of vanillin from lignin, phenolic stilbenes, isoeugenol, eugenol, guaicol, etc., with the disadvantage of harming the environment since these processes use strong oxidizing agents and toxic solvents. Thus, eco-friendly alternatives on the production of vanillin are very desirable and thus, under current investigation. Porous coordination polymers (PCPs) are a new class of highly crystalline materials that recently have been used for catalysis. HKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzene-tricarboxylate) is a very well known PCP which has been extensively studied as a heterogeneous catalyst. Here, we report a synthetic strategy for the production of vanillin by the oxidation of trans-ferulic acid using HKUST-1 as a catalyst.

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as Ru(II), Pt(II), and Rh(III). The compound, named as a water-soluble metal-organic complex array (WSMOCA), is obtained through 1) the conventional solution-chemistry-based preparation of the corresponding metal complex monomers having a 9-fluorenylmethyloxycarbonyl (Fmoc)-protected amino acid moiety and 2) their sequential coupling together with other water-soluble organic building units on the surface-functionalized polymeric resin by following the procedures originally developed for the solid-phase synthesis of polypeptides, with proper modifications. Traces of reactions determined by mass spectrometric analysis at the representative coupling steps in stage 2 confirm the selective construction of a predetermined sequence of metal centers along with the peptide backbone. The WSMOCA cleaved from the resin at the end of stage 2 has a certain level of solubility in aqueous media dependent on the pH value and/or salt content, which is useful for the purification of the compound.

Synthesis of a Water-soluble Metal&amp;#8211;Organic Complex Array

A potential general method for the synthesis of water-soluble multimetallic peptidic arrays containing a predetermined sequence of metal centers is presented.

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing to 250 &#176;C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 &#176;C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. These techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.

&#160; The protocol describes the synthesis and electrochemical testing of platinum-nickel nanowires. Nanowires were synthesized by the galvanic displacement of a nickel nanowire template. Post-synthesis processing, including hydrogen annealing, acid leaching, and oxygen annealing were used to optimize nanowire performance and durability in the oxygen reduction reaction.

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and porous metal-dithiolene network in the highly ordered single crystalline state. Unlike the highly reactive free-standing thiols, which tend to decompose and complicate the crystallization of metal-thiolate open frameworks, the thioester reacts in situ to provide the thiol species, serving to mitigate the reaction between the mercaptan units and the metal centers, and to improve crystallization consequently. Specifically, the thioester was synthesized in a one-pot procedure: an aromatic bromide (hexabromotriphenylene) reacted with excess sodium thiomethoxide under vigorous conditions to first form the thioether intermediate product. The thioether was then demethylated by the excess thiomethoxide to provide the thiolate anion that was acylated to form the thioester product. The thioester was conveniently purified by standard column chromatography, and then used directly in the framework synthesis, wherein NaOH and ethylenediamine serve to revert in situ the thioester to the thiol linker for assembling the single-crystalline Pb(II)-dithiolene network. Compared with other methods for thiol synthesis (e.g., by cleaving alkyl thioether using sodium metal and liquid ammonia), the thioester synthesis here uses simple conditions and economical reagents. Moreover, the thioester product is stable and can be conveniently handled and stored. More importantly, in contrast to the generic difficulty in accessing crystalline metal-thiolate open frameworks, we demonstrate that using the thioester for in situ formation of the thiol linker greatly improves the crystallinity of the solid-state product. We intend to encourage broader research efforts on the technologically important metal-sulfur frameworks by disclosing the synthetic protocol for the thioester as well as the crystalline framework solid.

Here, we present a one-pot, transition-metal-free synthesis of thiols and thioesters from aromatic halides and sodium thiomethoxide, followed by the preparation of single crystals of a metal-dithiolene network using thiol species generated in situ from the more stable and tractable thioester.

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and non-porous supports (polymer, ceramic, metal, carbon, and graphene). We developed a novel crystallization technique, which is termed the ENACT approach: the electrophoretic nuclei assembly for the crystallization of highly intergrown thin films (ENACT). This approach allows for a high density of heterogeneous nucleation of MOFs on a chosen substrate via the electrophoretic deposition (EPD) directly from the precursor sol. The growth of well-packed MOF nuclei leads to a highly intergrown polycrystalline MOF film. We show that this simple approach can be used for the synthesis of thin, intergrown zeolite imidazole framework (ZIF)-7 and ZIF-8 films. The resulting 500 nm-thick ZIF-8 membranes show a considerably high H2 permeance (8.3 x 10-6 mol m-2 s-1 Pa-1) and ideal gas selectivities (7.3 for H2/CO2, 15.5 for H2/N2, 16.2 for H2/CH4, and 2655 for H2/C3H8). An attractive performance for C3H6/C3H8 separation is also achieved (a C3H6 permeance of 9.9 x 10-8 mol m-2 s-1 Pa-1 and a C3H6/C3H8 ideal selectivity of 31.6 at 25 &#176;C). Overall, the ENACT process, owing to its simplicity, can be extended to synthesize intergrown thin films of a wide range of nanoporous crystalline materials.

A simple, reproducible, and versatile approach for the synthesis of intergrown, polycrystalline metal-organic framework membranes on a wide range of unmodified porous and non-porous supports is presented.

We report the synthesis of thin, highly intergrown, polycrystalline metal-organic framework (MOF) membranes on a wide range of unmodified porous and ...