Name: reverse microemulsion-mediated synthesis of monometallic and bimetallic early transition metal carbide and nitride nanoparticles
Uploaded: 2015-11-27T14:00:00
Description: Watch this Scientific Journal Video about Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles at JoVE.com

This work was sponsored by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, grant no. DE-FG02-12ER16352. S.T.H. thanks the National Science Foundation for financial support through the National Science Foundation Graduate Research Fellowship under Grant No. 1122374.

1. Synthesis of Silica-encapsulated Monometallic or Bimetallic Metal Oxide Nanoparticles
<ol>
	<li>Prepare the reverse microemulsion
	<ol>
		<li>Add 240 ml of anhydrous n-heptane to a clean, oven-dried 1 L round bottom flask (RBF) containing an oven-dried magnetic stir bar using a clean, oven-dried graduated cylinder.</li>
		<li>Add 54 ml of polyoxyethylene (4) lauryl ether to the n-heptane under constant stirring. 
		Note: Because of the high viscosity and low surface tension of this surfactant, a clean, dry 60 m...

<ol>
	<li>Oyama, S. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> The Chemistry of Transition Metal Carbides and Nitrides. , (1996).</li><li>Michalsky, R., Zhang, Y. -. J., Medford, A. J., Peterson, A. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Departures+from+the+Adsorption+Energy+Scaling+Relations+for+Metal+Carbide+Catalysts.">Departures from the Adsorption Energy Scaling Relations for Metal Carbide Catalysts.</a> J. Phys. Chem. C. 118 (24), 13026-13034 (2014).</li><li>Kimmel, Y. C., Xu, X., Yu, W., Yang, X., Chen, J. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Trends+in+Electrochemical+Stability+of+Transition+Metal+Carbides+and+Their+Potential+Use+As+Supports+for+Low-Cost+Electrocatalysts.">Trends in Electrochemical Stability of Transition Metal Carbides and Their Potential Use As Supports for Low-Cost Electrocatalysts.</a> ACS Catal. 4 (5), 1558-1562 (2014).</li><li>Levy, R. B., Boudart, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Platinum-like+behavior+of+tungsten+carbide+in+surface+catalysis.">Platinum-like behavior of tungsten carbide in surface catalysis.</a> Science. 181, 547-549 (1973).</li><li>Chen, Z., Higgins, D., Yu, A., Zhang, L., Zhang, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+review+on+non-precious+metal+electrocatalysts+for+PEM+fuel+cells.">A review on non-precious metal electrocatalysts for PEM fuel cells.</a> Energy Environ. Sci. 4 (9), 3167-3192 (2011).</li><li>Esposito, D. V., Chen, J. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Monolayer+platinum+supported+on+tungsten+carbides+as+low-cost+electrocatalysts:+opportunities+and+limitations.">Monolayer platinum supported on tungsten carbides as low-cost electrocatalysts: opportunities and limitations.</a> Energy Environ. Sci. 4, 3900 (2011).</li><li>Stottlemyer, A. L., Kelly, T. G., Meng, Q., Chen, J. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reactions+of+oxygen-containing+molecules+on+transition+metal+carbides:+Surface+science+insight+into+potential+applications+in+catalysis+and+electrocatalysis.">Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis.</a> Surf. Sci. Rep. 67, 201-232 (2012).</li><li>Bell, A. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+impact+of+nanoscience+on+heterogeneous+catalysis.">The impact of nanoscience on heterogeneous catalysis.</a> Science. 299, 1688-1691 (2003).</li><li>Kimmel, Y. C., Esposito, D. V., Birkmire, R. W., Chen, J. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+surface+carbon+on+the+hydrogen+evolution+reactivity+of+tungsten+carbide+(WC)+and+Pt-modified+WC+electrocatalysts.">Effect of surface carbon on the hydrogen evolution reactivity of tungsten carbide (WC) and Pt-modified WC electrocatalysts.</a> Int. J. Hydrogen Energy. 37, 3019-3024 (2012).</li><li>Yang, X., Kimmel, Y. C., Fu, J., Koel, B. E., Chen, J. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Activation+of+Tungsten+Carbide+Catalysts+by+Use+of+an+Oxygen+Plasma+Pretreatment.">Activation of Tungsten Carbide Catalysts by Use of an Oxygen Plasma Pretreatment.</a> ACS Catal. 2, 765-769 (2012).</li><li>Garcia-Esparza, A. T., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Tungsten+carbide+nanoparticles+as+efficient+cocatalysts+for+photocatalytic+overall+water+splitting.">Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting.</a> ChemSusChem. 6, 168-181 (2013).</li><li>Yan, Z., Cai, M., Shen, P. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanosized+tungsten+carbide+synthesized+by+a+novel+route+at+low+temperature+for+high+performance+electrocatalysis.">Nanosized tungsten carbide synthesized by a novel route at low temperature for high performance electrocatalysis.</a> Sci. Rep. 3, 1646 (2013).</li><li>Giordano, C., Erpen, C., Yao, W., Antonietti, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Mo+and+W+carbide+and+nitride+nanoparticles+via+a+simple+'urea+glass'+route.">Synthesis of Mo and W carbide and nitride nanoparticles via a simple 'urea glass' route.</a> Nano Lett. 8, 4659-4663 (2008).</li><li>Abdullaeva, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High+temperature+stable+WC1&#8722;x@C+and+TiC@C+core&#8211;shell+nanoparticles+by+pulsed+plasma+in+liquid.">High temperature stable WC1&#8722;x@C and TiC@C core&#8211;shell nanoparticles by pulsed plasma in liquid.</a> R. Soc. Chem. Adv. 3, 513 (2013).</li><li>Vallance, S. R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Probing+the+microwave+interaction+mechanisms+and+reaction+pathways+in+the+energy-efficient,+ultra-rapid+synthesis+of+tungsten+carbide.">Probing the microwave interaction mechanisms and reaction pathways in the energy-efficient, ultra-rapid synthesis of tungsten carbide.</a> Green Chem. 14, 2184 (2012).</li><li>Shen, P. K., Yin, S., Li, Z., Chen, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+and+performance+of+nanosized+tungsten+carbides+for+electrocatalysis.">Preparation and performance of nanosized tungsten carbides for electrocatalysis.</a> Electrochim. Acta. 55, 7969-7974 (2010).</li><li>Nikiforov, A. V., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=WC+as+a+non-platinum+hydrogen+evolution+electrocatalyst+for+high+temperature+PEM+water+electrolysers.">WC as a non-platinum hydrogen evolution electrocatalyst for high temperature PEM water electrolysers.</a> Int. J. Hydrogen Energy. 37, 18591-18597 (2012).</li><li>Fang, Z. Z., Wang, X., Ryu, T., Hwang, K. S., Sohn, H. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis,+sintering,+and+mechanical+properties+of+nanocrystalline+cemented+tungsten+carbide+&#8211;+A+review.">Synthesis, sintering, and mechanical properties of nanocrystalline cemented tungsten carbide &#8211; A review.</a> Int. J. Refract. Met. Hard Mater. 27, 288-299 (2009).</li><li>Liu, Y., Kelly, T. G., Chen, J. G., Mustain, W. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal+Carbides+as+Alternative+Electrocatalyst+Supports.">Metal Carbides as Alternative Electrocatalyst Supports.</a> ACS Catal. 3, 1184-1194 (2013).</li><li>Nie, M., Shen, P. K., Wei, Z. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanocrystaline+tungsten+carbide+supported+Au&#8211;Pd+electrocatalyst+for+oxygen+reduction.">Nanocrystaline tungsten carbide supported Au&#8211;Pd electrocatalyst for oxygen reduction.</a> J. Power Sources. 167 (1), 69-73 (2007).</li><li>Ham, D. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Palladium-nickel+alloys+loaded+on+tungsten+carbide+as+platinum-free+anode+electrocatalysts+for+polymer+electrolyte+membrane+fuel+cells.">Palladium-nickel alloys loaded on tungsten carbide as platinum-free anode electrocatalysts for polymer electrolyte membrane fuel cells.</a> Chem Commun (Camb). 47 (20), 5792-5794 (2011).</li><li>Yan, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Template-free+pseudomorphic+synthesis+of+tungsten+carbide+nanorods.">Template-free pseudomorphic synthesis of tungsten carbide nanorods.</a> Small. 8, 3350-3356 (2012).</li><li>Esposito, D. V., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Low-cost+hydrogen-evolution+catalysts+based+on+monolayer+platinum+on+tungsten+monocarbide+substrates.">Low-cost hydrogen-evolution catalysts based on monolayer platinum on tungsten monocarbide substrates.</a> Angew. Chem. Int. Ed. 49, 9859-9862 (2010).</li><li>Esposito, D. V., Hunt, S. T., Kimmel, Y. C., Chen, J. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+new+class+of+electrocatalysts+for+hydrogen+production+from+water+electrolysis:+metal+monolayers+supported+on+low-cost+transition+metal+carbides.">A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides.</a> J. Am. Chem. Soc. 134, 3025-3033 (2012).</li><li>Kelly, T. G., Hunt, S. T., Esposito, D. V., Chen, J. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Monolayer+palladium+supported+on+molybdenum+and+tungsten+carbide+substrates+as+low-cost+hydrogen+evolution+reaction+(HER)+electrocatalysts.">Monolayer palladium supported on molybdenum and tungsten carbide substrates as low-cost hydrogen evolution reaction (HER) electrocatalysts.</a> Int. J. Hydrogen Energy. 38, 5638-5644 (2013).</li><li>Hunt, S. T., Nimmanwudipong, T., Roman-Leshkov, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Engineering+non-sintered,+metal-terminated+tungsten+carbide+nanoparticles+for+catalysis.">Engineering non-sintered, metal-terminated tungsten carbide nanoparticles for catalysis.</a> Angew. Chem. Int. Ed. Engl. 53 (20), 5131-5136 (2014).</li><li>Mehrota, R. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Alkoxides+and+Alkylalkoxides+of+Metals+and+Metalloids.">Alkoxides and Alkylalkoxides of Metals and Metalloids.</a> Inorg. Chim. Acta. 1, 99-112 (1967).</li><li>Munoz-Aguado, M., Gregorkiewitz, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sol-Gel+Synthesis+of+Microporous+Amorphous+Silica+from+Purely+Inorganic+Precursors.">Sol-Gel Synthesis of Microporous Amorphous Silica from Purely Inorganic Precursors.</a> J. Colloid Interface Sci. 185, 459-465 (1997).</li></ol>

A procedure for synthesizing non-sintered, metal terminated transition metal carbide and nitride nanoparticles with tunable sizes and structure is presented here.26 Critical steps in the method include: using a moisture-free RBF to contain the diluted metal alkoxide precursor, avoiding alkali metal impurities during all steps, precipitating the RME with excess methanol as opposed to acetone or isopropanol, performing a proper leak check before carburizing or nitridizing the components, and using proper PPE whe...

Early transition metal carbides (TMCs) are low-cost, earth-abundant materials that exhibit high thermal and electrochemical stability as well as unique catalytic activities.1-3 In particular, tungsten carbide (WC) and molybdenum carbide (Mo2C) have been studied extensively for their catalytic similarities to the platinum group metals (PGMs).4,5 Due to these favorable properties, TMCs have been identified as candidates for replacing expensive PGM catalysts in emerging renewable energy technologies, such as biomass conversion, fuel cells, and electrolyzers.6,7
To maximize catalytic activity, commercial catalysts are almost always formulated as ultrasmall nanoparticles (diameters &#60;10 nm) dispersed on a high surface area support, such as carbon black.8 However, the synthesis of TMCs requires temperatures higher than ~700 &#176;C. This leads to extensive sintering of the nanoparticles (NPs), excess surface carbon deposition (coke), and thermal support degradation. Both particle sintering and support degradation lead to decreased material surface areas. Excess surface impurity deposition blocks active metal sites, which has been shown to greatly reduce or in some instances completely eliminate the catalytic activity of TMCs.9,10 As such, the fundamental study of TMC reactivity is predominantly performed on bulk microparticles or thin films with finely controlled surfaces rather than on high surface area TMC nanomaterials.
Many methods have been developed to synthesize TMC NPs, but these methods are not suitable for synthesizing catalytically active TMC NPs. Traditional wet impregnation techniques use metal salt solutions impregnated on a high surface area support. On heating, wet impregnation methods can expose the catalyst support to destructive carburizing conditions leading to support degradation. Furthermore, sintering can only be mitigated at low wt% loadings of the metal on the support, and it is also not possible to synthesize unsupported TMC nanopowders using wet impregnation. Several newer methods involve mixing a metal precursor with a carbon precursor and applying conventional and unconventional heating techniques.11-18 Excess carbon is used to prevent sintering, but this excess carbon results in extensive surface carbon, making these materials not suitable for catalytic applications.
Due to these synthetic challenges, TMCs have traditionally been studied as co-catalysts11 for PGMs, catalyst supports for PGMs,19-22 or supports for active PGM monolayers.23-25 The method presented here offers the ability to synthesize both non-sintered and metal-terminated TMC NPs as well as transition metal nitride (TMN) NPs with tunable sizes, crystalline phases, and metallic composition.26 The method presented also offers the ability to obtain TMC or TMN nanodispersions or deposit the TMC and TMN NPs on a high surface area catalyst support at room-temperature, thereby mitigating thermal support degradation. This method is therefore suitable for standalone catalytic applications of TMC and TMN NPs, the development of advanced multimetallic TMC and TMN NPs, or other applications requiring finely controlled particle sizes and surfaces.26
The method presented here uses a three step protocol to synthesize TMC and TMN NPs. In the first step, a reverse microemulsion (RME) is used to coat early transition metal oxide (TMO) NPs in silica nanospheres. The emulsion is prepared by dispersing water droplets in a nonpolar medium using a commercial nonionic surfactant. The silica-encapsulated TMO NPs are then subjected to either carburizing or nitridizing heat treatments. Here, the silica prevents particle sintering at high temperatures while allowing the reactive gases to diffuse to the TMO NPs and convert them to TMC or TMN NPs. In the final step, the silica shells are removed using either acidic or alkaline treatment to obtain TMC or TMN nanodispersions that can be dispersed on a high surface area support, such as carbon black.

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>n-heptane</td>
			<td>Sigma-Aldrich</td>
			<td>246654</td>
			<td></td>
		</tr>
		<tr>
			<td>polyoxyethylene (4) lauryl ether</td>
			<td>Sigma-Aldrich</td>
			<td>235989</td>
			<td>Brij&#174; L4</td>
		</tr>
		<tr>
			<td>tungsten (VI) isopropoxide</td>
			<td>Alfa Aesar</td>
			<td>40247</td>
			<td>W(VI)IPO</td>
		</tr>
		<tr>
			<td>tungsten (VI) chloride</td>
			<td>Sigma-Aldrich</td>
			<td><a href="http://www.sigmaaldrich.com/catalog/product/aldrich/241911?lang=en&amp;region=US">241911</a></td>
			<td>To prepare W(VI)IPO, homemade</td>
		</tr>
		<tr>
			<td>tungsten (IV) chloride</td>
			<td>Strem Chemicals</td>
			<td>74-2348</td>
			<td>To prepare W(IV)IPO, homemade</td>
		</tr>
		<tr>
			<td>tantalum (V) isopropoxide</td>
			<td>Alfa Aesar</td>
			<td><a href="http://www.alfa.com/en/catalog/40038">40038</a></td>
			<td>Ta(V)IPO</td>
		</tr>
		<tr>
			<td>niobium (V) isopropoxide</td>
			<td>Alfa Aesar</td>
			<td><a href="http://www.alfa.com/en/catalog/36572">36572</a></td>
			<td>Nb(V)IPO</td>
		</tr>
		<tr>
			<td>nickel (II) methoxyethoxide</td>
			<td>Alfa Aesar</td>
			<td>42377</td>
			<td>Ni(II)MEO</td>
		</tr>
		<tr>
			<td>titanium (IV) isopropoxide</td>
			<td>Sigma-Aldrich</td>
			<td><a href="http://www.sigmaaldrich.com/catalog/product/aldrich/87560?lang=en&amp;region=US">87560</a></td>
			<td>Ti(IV)IPO</td>
		</tr>
		<tr>
			<td>molybdenum (V) isopropoxide</td>
			<td>Alfa Aesar</td>
			<td><a href="http://www.alfa.com/en/catalog/39159">39159</a></td>
			<td>Mo(V)IPO</td>
		</tr>
		<tr>
			<td>molybdenum (V) chloride</td>
			<td>Sigma-Aldrich</td>
			<td><a href="http://www.sigmaaldrich.com/catalog/product/aldrich/208353?lang=en&amp;region=US">208353</a></td>
			<td>To prepare Mo(V)IPO, homemade</td>
		</tr>
		<tr>
			<td>tetraethyl orthosilicate</td>
			<td>Sigma-Aldrich</td>
			<td>333859</td>
			<td>TEOS</td>
		</tr>
		<tr>
			<td>ammonium hydroxide</td>
			<td>Sigma-Aldrich</td>
			<td>320145</td>
			<td></td>
		</tr>
		<tr>
			<td>methanol</td>
			<td>Sigma-Aldrich</td>
			<td>34860</td>
			<td></td>
		</tr>
		<tr>
			<td>anhydrous isopropanol</td>
			<td>Sigma-Aldrich</td>
			<td><a href="http://www.sigmaaldrich.com/catalog/product/sial/278475?lang=en&amp;region=US">278475</a></td>
			<td>To prepare homemade alkoxides</td>
		</tr>
		<tr>
			<td>ammonium bifluoride</td>
			<td>Sigma-Aldrich</td>
			<td>224820</td>
			<td></td>
		</tr>
		<tr>
			<td>carbon black</td>
			<td>Cabot Corp.</td>
			<td>Vulcan&#174; XC72R</td>
			<td></td>
		</tr>
		<tr>
			<td>Methane</td>
			<td>AirGas</td>
			<td>ME R300</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrogen</td>
			<td>AirGas</td>
			<td>HY UHP300</td>
			<td></td>
		</tr>
		<tr>
			<td>Ammonia</td>
			<td>AirGas</td>
			<td>AM AH80N705</td>
			<td></td>
		</tr>
		<tr>
			<td>Quartz Tube Furnace</td>
			<td>MTI Corp.</td>
			<td>OTF-1200X-S-UL</td>
			<td></td>
		</tr>
	</tbody>
</table>

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

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.

In the first step of the protocol, the goal is to encapsulate the monometallic or bimetallic transition metal oxide (TMO) NPs within microporous silica spheres. Figure 1 shows images taken of representative syntheses before and after precipitation with methanol. Two reproducible morphological outcomes have been observed during this step that appear to be dependent on the metals used in the synthesis: the TMO NPs can be singly coated with a silica sphere (Figure 2b) or multiple TMO NPs ca...

Watch this Scientific Journal Video about Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles at JoVE.com

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 structures.

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

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The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution ...

Synthesis of Bimetallic Pt/Sn-based Nanoparticles in Ionic Liquids

We demonstrate a method for the synthesis of bimetallic nanoparticles consisting of Pt and Sn. A synthesis strategy is used in which the particular ...

Molten-Salt Synthesis of Complex Metal Oxide Nanoparticles

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. ...

Synthesis and Characterization of Amphiphilic Gold Nanoparticles

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of ...

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

Heteroarylation introduces heteroaryl fragments to organic molecules. Despite the numerous available reactions reported for arylation via transition metal ...