This work was supported by the Department of Energy Bioenergy Technologies Office under Contract no. DE-AC36-08-GO28308. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.

<ol>
	<li>Cvetanovi&#263;, R. J., Amenomiya, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Application+of+a+Temperature-Programmed+Desorption+Technique+to+Catalyst+Studies.">Application of a Temperature-Programmed Desorption Technique to Catalyst Studies.</a> Adv. Catal. 17, 103-149 (1967).</li><li>Falconer, J. L., Schwarz, J. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Temperature-Programmed+Desorption+and+Reaction:+Applications+to+Supported+Catalysts.">Temperature-Programmed Desorption and Reaction: Applications to Supported Catalysts.</a> Catal. Rev. - Sci. Eng. 25 (2), 141-227 (1983).</li><li>Hurst, N. W., Gentry, S. J., Jones, A., McNicol, B. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Temperature+Programmed+Reduction.">Temperature Programmed Reduction.</a> Catal. Rev. - Sci. Eng. 24 (2), 233-309 (1982).</li><li>Sanchez, A., 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=When+Gold+Is+Not+Noble:+Nanoscale+Gold+Catalysts.">When Gold Is Not Noble: Nanoscale Gold Catalysts.</a> J. Phys. Chem. A. 103 (48), 9573-9578 (1999).</li><li>Alayoglu, S., Nilekar, A. U., Mavrikakis, M., Eichhorn, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ru-Pt+core-shell+nanoparticles+for+preferential+oxidation+of+carbon+monoxide+in+hydrogen.">Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen.</a> Nat Mater. 7 (4), 333-338 (2008).</li><li>Wachs, I. E., Madix, R. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+oxidation+of+methanol+on+a+silver+(110)+catalyst.">The oxidation of methanol on a silver (110) catalyst.</a> Surf. Sci. 76 (2), 531-558 (1978).</li><li>Topsoe, N. Y., Topsoe, H., Dumesic, J. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vanadia/Titania+Catalysts+for+Selective+Catalytic+Reduction+(SCR)+of+Nitric-Oxide+by+Ammonia.">Vanadia/Titania Catalysts for Selective Catalytic Reduction (SCR) of Nitric-Oxide by Ammonia.</a> J Catal. 151 (1), 226-240 (1995).</li><li>Clarke, D. B., 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=An+Infrared+Study+of+Methanol+Synthesis+from+CO2+on+Clean+and+Potassium-Promoted+Cu/SiO2.">An Infrared Study of Methanol Synthesis from CO2 on Clean and Potassium-Promoted Cu/SiO2.</a> J Catal. 154 (2), 314-328 (1995).</li><li>Schaidle, J. A., 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=Experimental+and+Computational+Investigation+of+Acetic+Acid+Deoxygenation+over+Oxophilic+Molybdenum+Carbide:+Surface+Chemistry+and+Active+Site+Identity.">Experimental and Computational Investigation of Acetic Acid Deoxygenation over Oxophilic Molybdenum Carbide: Surface Chemistry and Active Site Identity.</a> ACS Catal. 6 (2), 1181-1197 (2016).</li><li>Ruddy, D. A., 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=Recent+advances+in+heterogeneous+catalysts+for+bio-oil+upgrading+via+"ex+situ+catalytic+fast+pyrolysis":+catalyst+development+through+the+study+of+model+compounds.">Recent advances in heterogeneous catalysts for bio-oil upgrading via "ex situ catalytic fast pyrolysis": catalyst development through the study of model compounds.</a> Green Chem. 16 (2), 454-490 (2014).</li><li>Dutta, A., Schaidle, J. A., Humbird, D., Baddour, F. G., Sahir, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conceptual+Process+Design+and+Techno-Economic+Assessment+of+Ex+Situ+Catalytic+Fast+Pyrolysis+of+Biomass:+A+Fixed+Bed+Reactor+Implementation+Scenario+for+Future+Feasibility.">Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility.</a> Top. Catal. 59 (1), 2-18 (2016).</li><li>Venkatakrishnan, V. K., Delgass, W. N., Ribeiro, F. H., Agrawal, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Oxygen+removal+from+intact+biomass+to+produce+liquid+fuel+range+hydrocarbons+via+fast-hydropyrolysis+and+vapor-phase+catalytic+hydrodeoxygenation.">Oxygen removal from intact biomass to produce liquid fuel range hydrocarbons via fast-hydropyrolysis and vapor-phase catalytic hydrodeoxygenation.</a> Green Chem. 17 (1), 178-183 (2015).</li><li>Bej, S. K., Thompson, L. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Acetone+condensation+over+molybdenum+nitride+and+carbide+catalysts.">Acetone condensation over molybdenum nitride and carbide catalysts.</a> Appl. Catal., A. 264 (2), 141-150 (2004).</li><li>Sullivan, M. M., Held, J. T., Bhan, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structure+and+site+evolution+of+molybdenum+carbide+catalysts+upon+exposure+to+oxygen.">Structure and site evolution of molybdenum carbide catalysts upon exposure to oxygen.</a> J Catal. 326, 82-91 (2015).</li><li>Lee, W. S., Kumar, A., Wang, Z. S., Bhan, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chemical+Titration+and+Transient+Kinetic+Studies+of+Site+Requirements+in+Mo2C-Catalyzed+Vapor+Phase+Anisole+Hydrodeoxygenation.">Chemical Titration and Transient Kinetic Studies of Site Requirements in Mo2C-Catalyzed Vapor Phase Anisole Hydrodeoxygenation.</a> ACS Catal. 5 (7), 4104-4114 (2015).</li><li>Ren, H., 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=Selective+Hydrodeoxygenation+of+Biomass-Derived+Oxygenates+to+Unsaturated+Hydrocarbons+using+Molybdenum+Carbide+Catalysts.">Selective Hydrodeoxygenation of Biomass-Derived Oxygenates to Unsaturated Hydrocarbons using Molybdenum Carbide Catalysts.</a> Chemsuschem. 6 (5), 798-801 (2013).</li><li>Grob, R. L., Kaiser, M. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Modern Practice of Gas Chromatography. , 403-460 (2004).</li><li>Guiochon Georges, L., Guillemin Claude, <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Journal of Chromatography Library. 42, 563-586 (1988).</li><li>Guiochon Georges, L., Guillemin Claude, <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Journal of Chromatography Library. 42, 587-627 (1988).</li><li>Guiochon Georges, L., Guillemin Claude, <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Journal of Chromatography Library. 42, 629-659 (1988).</li><li>Guiochon Georges, L., Guillemin Claude, <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Journal of Chromatography Library. 42, 661-687 (1988).</li><li>Baddour, F. G., Nash, C. P., Schaidle, J. A., Ruddy, D. A. <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+&#945;-MoC1-x+Nanoparticles+with+a+Surface-Modified+SBA-15+Hard+Template:+Determination+of+Structure-Function+Relationships+in+Acetic+Acid+Deoxygenation.">Synthesis of &#945;-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation.</a> Angew. Chem., Int. Ed. n/a-n/a. , (2016).</li><li>Habas, S. E., 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=A+Facile+Molecular+Precursor+Route+to+Metal+Phosphide+Nanoparticles+and+Their+Evaluation+as+Hydrodeoxygenation+Catalysts.">A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts.</a> Chem. Mater. 27 (22), 7580-7592 (2015).</li><li>Zhang, Q., 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=Deconvolution+and+quantification+of+hydrocarbon-like+and+oxygenated+organic+aerosols+based+on+aerosol+mass+spectrometry.">Deconvolution and quantification of hydrocarbon-like and oxygenated organic aerosols based on aerosol mass spectrometry.</a> Environ Sci Technol. 39 (13), 4938-4952 (2005).</li><li>Ko, E. I., Benziger, J. B., Madix, R. J. <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+Methanol+on+W(100)+and+W(100)-(5+X+1)C+Surfaces.">Reactions of Methanol on W(100) and W(100)-(5 X 1)C Surfaces.</a> J Catal. 62 (2), 264-274 (1980).</li><li>Pestman, R., Koster, R. M., Pieterse, J. A. Z., Ponec, V. <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+carboxylic+acids+on+oxides:+1.+Selective+hydrogenation+of+acetic+acid+to+acetaldehyde.">Reactions of carboxylic acids on oxides: 1. Selective hydrogenation of acetic acid to acetaldehyde.</a> J Catal. 168 (2), 255-264 (1997).</li><li>Pestman, R., Koster, R. M., Van Duijne, A., Pieterse, J. A. Z., Ponec, V. <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+carboxylic+acids+on+oxides:+2.+Bimolecular+reaction+of+aliphatic+acids+to+ketones.">Reactions of carboxylic acids on oxides: 2. Bimolecular reaction of aliphatic acids to ketones.</a> J Catal. 168 (2), 265-272 (1997).</li><li>. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=NIST+Standard+Reference+Database+Number+69.">NIST Standard Reference Database Number 69.</a> NIST Chemistry WebBook. , (2016).</li><li>Ausloos, P., 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=The+critical+evaluation+of+a+comprehensive+mass+spectral+library.">The critical evaluation of a comprehensive mass spectral library.</a> J. Am. Soc. Mass Spectrom. 10 (4), 287-299 (1999).</li><li>Barwick, V., Langley, J., Mallet, T., Stein, B., Webb, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Best Practice Guide for Generating Mass Spectra. , (2006).</li><li>Lecchi, P., 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=A+Method+for+Monitoring+and+Controlling+Reproducibility+of+Intensity+Data+in+Complex+Electrospray+Mass+Spectra:+A+Thermometer+Ion-based+Strategy.">A Method for Monitoring and Controlling Reproducibility of Intensity Data in Complex Electrospray Mass Spectra: A Thermometer Ion-based Strategy.</a> J. Am. Soc. Mass Spectrom. 20 (3), 398-410 (2009).</li></ol>

The authors have nothing to disclose.

TPRxn方法は、反応温度の関数として触媒の活性及び選択性に関する情報を提供する、触媒物質のスクリーニングのための強力なツールです。このようなTPD、TPOおよびTPRのような他の昇温方法は、反応物質の吸着力、吸着サイトの数、および適切な触媒の前処理手順に関する情報を提供することができますが、直接触媒性能データを提供していません。なお、この作業で詳述TPRxn方法が定常状?...

温度プログラム反応（TPRxn）を、反応物の同時に脱着（TPD）、酸化（TPO）、及び還元（TPR）を含む多くの昇温方法の一つであり、触媒の暴露を介して進行しているかが着実に増加が続きます温度。 1、2、3 TPRxnは、反応温度の関数としての触媒活性及び選択性に関する情報を提供する過渡的な技術です。 4、5、6また、人気の技術です：文学利回りその使用を理由に1000人以上のソース中のキーワード「昇温反応」の検索。 TPRxn実験は、典型的には、反応器流出物とpの相関のリアルタイム分析のために質量分析計（MS）を備えたマイクロリアクターシステムで実施されます温度とerformance。反応ガスは、マスフローコントローラと液体が液体を介して不活性ガスをバブリングすることにより、シリンジポンプを介して、又は蒸気として導入することができる使用して導入することができます。触媒は、多くの場合、反応のための所望の触媒相を形成するために、その場で前処理されます。いくつかのシステムは、触媒、または反応機構上に存在する触媒選択、表面種に関する定量的または定性的な情報を提供するために、典型的な質量分析計を超えて、追加の分析機器が装備されています。例えば、 その場フーリエ変換にプログラムされた温度は、赤外分光法（FTIR）を、反応温度を変化させた表面種の進化に関する情報を提供変換します。 図7に示すように 、この研究で実証8 TPRxnシステムは、より一般的なMSに加えて、ガスクロマトグラム（GC）を備えています。 4つの並列列を装備したこのGCは、より正確な定量化を可能にします反応生成物のfication、それはカラムを通って溶出する製品にかかる時間によって解析周波数に制限されています。したがって、MSおよびGCの組み合わせは、反応物及び生成物の正確な定量化のリアルタイム識別を結合するために特に有用であり得ます。 ここでは、炭化モリブデン触媒上での酢酸の脱酸素化を研究するためにTPRxnの方法論を適用します。酢酸はバイオマス熱分解蒸気中に存在する多くのカルボン酸のために有用なアナログであるように、これは、触媒の研究で興味深いと重要な反応です。 9バイオマス熱分解蒸気の高い酸素含有量は、炭化水素燃料を生成するために、酸素除去を必要と10、11、12、炭化モリブデン触媒は、フルフラールを含む多くのバイオマス熱分解蒸気のモデル化合物、1-プロパノールを約束脱酸素性能を示していますフェノールおよび酢酸。 9、13、14、15、16が、脱酸素反応における炭化モリブデン触媒の活性および選択性は、触媒の構造と組成、反応種と反応条件に依存します。 酢酸のTPRxnから収集されたデータは、炭化モリブデン触媒は、 約上記の脱酸素反応のために活性であることを示しています300℃であり、触媒の特性情報と組み合わせた酢酸の代謝回転率の計算を介して、温度の関数としての触媒活性の定量化を可能にします。 TPRxn結果は、脱酸素化（ すなわち 、COの結合破壊）製品は、約以下の温度で好まれていることを示しています400℃、脱カルボニル化（ すなわち 、CC結合破壊）製品はFAVOです約以上の温度での赤400°C。さらに、TPRxn研究は、種々の合成手順（ すなわち 、別のモリブデンカーバイド触媒の構造と組成物の製造）を用いて製造炭化モリブデン触媒の活性および選択性の変化を示します。それでも、この情報の値は、より一般的に、触媒の設計およびプロセスの最適化に向けTPRxn実験データの成功した適用は、得られるデータの質の関数です。 TPRxn手順を通して強調された潜在的な難しさや限界を慎重に検討し、知識が最も重要です。

<table><tbody><tr><td>glacial acetic acid</td><td>Cole-Parmer</td><td>EW-88401-62</td><td>alternate supplier acceptable if ACS purity grade. See caution statement in protocol for safety information</td></tr><tr><td>UHP He</td><td>Airgas</td><td>HE R300SS</td><td>alternate supplier acceptable if&amp;nbsp;&gt;99.99% purity</td></tr><tr><td>UHP Ar</td><td>Arigas</td><td>AR R200</td><td>alternate supplier acceptable if&amp;nbsp;&gt;99.99% purity</td></tr><tr><td>acetone</td><td>VWR International</td><td>BDH1101-4LP</td><td>alternate supplier acceptable if&amp;nbsp;&gt;99.5% purity</td></tr><tr><td>quartz chips</td><td>Powder Technology Inc.</td><td>Crushed Quartz</td><td>sieved 180-300 &amp;micro;m, calcined in air at 500 &amp;deg;C overnight</td></tr><tr><td>mass spectrometer - turbo vacuum pump</td><td>Pfeiffer Vacuum</td><td>TSU 071</td><td>mass spectrometer is controlled with LabVIEW 2010 software package (National Instruments)</td></tr><tr><td>mass spectrometer - turbo vacuum pump</td><td>Stanford Research Systems</td><td>RGA100</td><td></td></tr><tr><td>micro gas chromatograph</td><td>Agilent</td><td>CP740388</td><td>490 Micro GC; 4-channel system&lt;br/&gt; Channel 1: 494001360 Molseive 10m, heated backflush&lt;br/&gt; Channel 2: 494001460 PPU 10m, heated backflush&lt;br/&gt; Channel 3: 490040 AL2O3/KCL 10+0.2m, heated backflush SPECIAL&lt;br/&gt; Channel 4: 492005750 5CB 15m, heated</td></tr><tr><td>GC software</td><td>Aglient</td><td>OpenLAB CDS EZChrom Edition</td><td></td></tr><tr><td>clean gas filters</td><td>Agilent</td><td>CP17974</td><td>for use on GC carrier gases (He, Ar)</td></tr><tr><td>quartz &quot;U-tube&quot; reactor</td><td>n/a</td><td></td><td>hand blown glass, custom built to order</td></tr><tr><td>bubbler</td><td>n/a</td><td></td><td>custom built to order</td></tr><tr><td>ceramic furnace</td><td>Watlow</td><td>discontinued</td><td>Similar furnace part #: VC401J12A-B000R</td></tr><tr><td>heat tape controller</td><td>n/a</td><td></td><td>custom built with Watlow EZ-zone parts</td></tr><tr><td>heat tape</td><td>Omega</td><td>FGH051-060</td><td>alternate supplier for extreme temperature heat tape acceptable</td></tr><tr><td>heat tape insulation</td><td>JEGS</td><td>710-80809</td><td>alternate supplier acceptable</td></tr><tr><td>thermocouple</td><td>Omega</td><td>&lt;em&gt;e.g.&lt;/em&gt;, KMQSS-062U-18</td><td>K-type thermocouples; alternate sizes may be required</td></tr><tr><td>thermocouple O-ring</td><td>Swagelok</td><td>VT-7-OR-001-1/2</td><td>perfluoroelastomer(fluorocarbon FKM) O-ring</td></tr><tr><td>2 &amp;micro;m solids filter, VCR gasket</td><td>Swagelok</td><td>SS-4-VCR-2-2M</td><td></td></tr><tr><td>1 &amp;micro;m orifice, VCR gasket</td><td>Lenox Laser</td><td>SS-4-VCR-2</td><td>for mass spectrometer orifice</td></tr><tr><td>316/316L stainless steel tubing and fittings</td><td>Swagelok</td><td>Varies</td><td>See Swagelok &#039;VCR Metal Gasket Face Seal Fittings&#039; and &#039;Stainless Steel Seamless Tubing and Tube Support Systems&#039; catalogs for more information</td></tr><tr><td>316/316L stainless steel tubing and fittings</td><td>Swagelok</td><td>Varies</td><td>See Swagelok &#039;Integral-Bonnet Needle Valves&#039;, &#039;Bellows-Sealed Valves&#039; and &#039;One-Piece Instrumentation Ball Valves&#039; catalogs for more information</td></tr></tbody></table>

temperature-programmed deoxygenation of acetic acid on molybdenum carbide catalysts

温度プログラム反応（TPRxn）は、種々の条件で固体触媒性能をスクリーニングするためのシンプルで強力なツールです。 TPRxnシステムは、実時間（ 例えば 、質量分析計）で反応を監視するために、反応生成物（ 例えば 、ガスクロマトグラフ）、および計測を定量化するために、機器を制御するフロー反応器、炉、ガスおよび蒸気の供給源を含みます。ここでは、酢酸、バイオマス熱分解蒸気のアップグレード/安定化には多くの中で重要な反応の脱酸素化のためのモリブデン炭化物触媒を研究するTPRxnの方法論を適用します。 TPRxnは、触媒活性および選択性を評価し、仮想的な反応経路（ 例えば 、脱カルボニル化、ケトン化および水素化）をテストするために使用されます。酢酸脱酸素のTPRxn試験の結果は、炭化モリブデンは約以上の温度で、この反応のための活性な触媒であることを示し300℃、反応の好意こと約以下の温度で脱酸素化（ すなわち 、COの結合破壊）製品約以上の温度で400°Cと脱カルボニル化（ すなわち 、CCの結合破壊）製品400°C。

オンラインMSは、リアルタイムで反応器出口ガス組成を分析する能力を提供します。オンラインMS分析前に別々の製品への任意の装置と結合し、従って、重複質量断片化パターンを有する化合物とを区別する際に、種の識別が困難である。されていません表2に示すように 、酢酸TPRxn実験から共通の製品の多くは、複数の共通のm / zシグナルに?...

Watch this Scientific Journal Video about Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts at JoVE.com

Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts

酢酸の脱酸素中に、炭化モリブデンの触媒性能を評価するためのマイクロスケールの温度プログラム原子炉の運転のためのプロトコルは、ここに提示しました。

モリブデンカーバイド触媒上の酢酸の昇温脱酸素化

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system ...

temperature-programmed-deoxygenation-acetic-acid-on-molybdenum

Universidad de Cartagena UDEC

Research

Education

JoVE Journal

JoVE Core

Organic Chemistry

Chemistry

Unit 1

Thermodynamics and Chemical Kinetics

SCIENTISTS IN ACTION

11.4K ビュー.  National Renewable Energy Laboratory. 酢酸の脱酸素中に、炭化モリブデンの触媒性能を評価するためのマイクロスケールの温度プログラム原子炉の運転のためのプロトコルは、ここに提示しました。 

ビデオ: Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts

Aerosol-assisted Chemical Vapor Deposition of Metal Oxide Structures: Zinc Oxide Rods

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, their high cost production and/or incompatibility with microfabrication technologies, due to the use of pre-deposited catalyst-seeds and/or high processing temperatures exceeding 900 &#176;C, represent a drawback for a widespread use of these methods. Here, however, we report the synthesis of ZnO rods via a non-catalyzed vapor-solid mechanism enabled by using an aerosol-assisted chemical vapor deposition (CVD) method at 400 &#176;C with zinc chloride (ZnCl2) as the precursor and ethanol as the carrier solvent. This method provides both single-step formation of ZnO rods and the possibility of their direct integration with various substrate types, including silicon, silicon-based micromachined platforms, quartz, or high heat resistant polymers. This potentially facilitates the use of this method at a large-scale, due to its compatibility with state-of-the-art microfabrication processes for device manufacture. This report also describes the properties of these structures (e.g., morphology, crystalline phase, optical band gap, chemical composition, electrical resistance) and validates its gas sensing functionality towards carbon monoxide.

Columnar zinc oxide structures in the form of rods are synthesized via aerosol-assisted chemical vapor deposition without the use of pre-deposited catalyst-seed particles. This method is scalable and compatible with various substrates based on either silicon, quartz or polymers.

エアロゾルによる金属酸化物の構造の化学蒸着: 酸化亜鉛棒

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, ...

化学

Simultaneous Multi-surface Anodizations and Stair-like Reverse Biases Detachment of Anodic Aluminum Oxides in Sulfuric and Oxalic Acid Electrolyte

After reporting on the two-step anodization, nanoporous anodic aluminum oxides (AAOs) have been widely utilized in the versatile fields of fundamental sciences and industrial applications owing to their periodic arrangement of nanopores with relatively high aspect ratio. However, the techniques reported so far, which could be only valid for mono-surface anodization, show critical disadvantages, i.e., time-consuming as well as complicated procedures, requiring toxic chemicals, and wasting valuable natural resources. In this paper, we demonstrate a facile, efficient, and environmentally clean method to fabricate nanoporous AAOs in sulfuric and oxalic acid electrolytes, which can overcome the limitations that result from conventional AAO fabricating methods. First, plural AAOs are produced at one time through simultaneous multi-surfaces anodization (SMSA), indicating mass-producibility of the AAOs with comparable qualities. Second, those AAOs can be separated from the aluminum (Al) substrate by applying stair-like reverse biases (SRBs) in the same electrolyte used for the SMSAs, implying simplicity and green technological characteristics. Finally, a unit sequence consisting of the SMSAs sequentially combined with SRBs-based detachment can be applied repeatedly to the same Al substrate, which reinforces the advantages of this strategy and also guarantees the efficient usage of natural resources.

A protocol for fabricating nanoporous anodic aluminum oxides via simultaneous multi-surfaces anodization followed by stair-like reverse biases detachments is presented. It can be applied repeatedly to the same aluminum substrate, exhibiting a facile, high-yield, and environmentally clean strategy.

同時マルチ表面 Anodizations、階段のような逆バイアスで硫酸陽極酸化アルミニウムとシュウ酸電解質の剥離

After reporting on the two-step anodization, nanoporous anodic aluminum oxides (AAOs) have been widely utilized in the versatile fields of fundamental ...

工学

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.

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.

合成と電気化学的 CO2削減のため単一原子の遷移金属触媒の性能評価

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

Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model

Vanadium dioxide is a material that has a reversible metal-insulator phase change near 68 &#176;C. To grow VO2 on a wide variety of substrates, with wafer-scale uniformity and angstrom level control of thickness, the method of atomic-layer deposition was chosen. This ALD process enables high-quality, low-temperature (&#8804;150 &#176;C) growth of ultrathin films (100-1000 &#197;) of VO2. For this demonstration, the VO2 films were grown on sapphire substrates. This low temperature growth technique produces mostly amorphous VO2 films. A subsequent anneal in an ultra-high vacuum chamber with a pressure of 7x10-4 Pa of ultra-high purity (99.999%) oxygen produced oriented, polycrystalline VO2 films. The crystallinity, phase, and strain of the VO2 were determined by Raman spectroscopy and X-ray diffraction, while the stoichiometry and impurity levels were determined by X-ray photoelectron spectroscopy, and finally the morphology was determined by atomic force microscopy. These data demonstrate the high-quality of the films grown by this technique. A model was created to fit to the data for VO2 in its metallic and insulating phases in the near infrared spectral region. The permittivity and refractive index of the ALD VO2 agreed well with the other fabrication methods in its insulating phase, but showed a difference in its metallic state. Finally, the analysis of the films&#39; optical properties enabled the creation of a wavelength- and temperature-dependent model of the complex optical refractive index for developing VO2 as a tunable refractive index material.

Thin films (100-1000 &#197;) of vanadium dioxide (VO2) were created by atomic-layer deposition (ALD) on sapphire substrates. Following this, the optical properties were characterized through the metal-insulator transition of VO2. From the measured optical properties, a model was created to describe the tunable refractive index of VO2.

二酸化バナジウムと温度依存性の光学モデルの原子層堆積法

Vanadium dioxide is a material that has a reversible metal-insulator phase change near 68 &#176;C. To grow VO2 on a wide variety of substrates, with ...

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven effective in gas adsorption, separations, and catalysis. MOFs are most commonly synthesized as bulk powder, requiring additional processes to adhere them to functional devices and fabrics that risk decreasing the powder porosity and adsorption capacity. Here, we demonstrate a method of first coating fabrics with metal oxide films using atomic layer deposition (ALD). This process creates conformal films of controllable thickness on each fiber, while providing a more reactive surface for MOF nucleation. By submerging the ALD coated fabric in solution during solvothermal MOF synthesis, the MOFs create a conformal, well-adhered coating on the fibers, resulting in a MOF-functionalized fabric, without additional adhesion materials that may block MOF pores and functional sites. Here we demonstrate two solvothermal synthesis methods. First, we form a MIL-96(Al) layer on polypropylene fibers using synthetic conditions that convert the metal oxide to MOF. Using initial inorganic films of varying thicknesses, diffusion of the organic linker into the inorganic allows us to control the extent of MOF loading on the fabric. Second, we perform a solvothermal synthesis of UiO-66-NH2 in which the MOF nucleates on the conformal metal oxide coating on polyamide-6 (PA-6) fibers, thereby producing a uniform and conformal thin film of MOF on the fabric. The resulting materials can be directly incorporated into filter devices or protective clothing and eliminate the maladroit qualities of loose powder.

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks are effective in gas storage and heterogeneous catalysis, but typical synthesis methods result in loose powders that are difficult to incorporate into smart materials. We demonstrate a method of first coating fabrics with ALD metal oxides, resulting in conformal films of MOF on the fabrics during solvothermal synthesis.

ミル-96、UiO-66-NH2原子層のソルボサーマル合成繊維のマット上金属酸化皮膜に堆積

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Herein is presented a general strategy to perform reactions under mild to moderate CO2 pressures with dry ice. This technique obviates the need for specialized equipment to achieve modest pressures, and can even be used to achieve higher pressures in more specialized equipment and sturdier reaction vessels. At the end of the reaction, the vials can be easily depressurized by opening at room temperature. In the present example CO2 serves as both a putative directing group as well as a way to passivate amine substrates, thereby preventing oxidation during the organometallic reaction. In addition to being easily added, the directing group is also removed under vacuum, obviating the need for extensive purification to remove the directing group. This strategy allows the facile &#947;-C(sp3)-H arylation of aliphatic amines and has the potential to be applied to a variety of other amine-based reactions.

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Here we present a protocol for performing reactions in simple reaction vessels under low-to-moderate pressures of CO2. The reactions can be performed in a variety of vessels simply by administering the carbon dioxide in the form of dry ice, without the need for costly or elaborate equipment or set-ups.

固体 CO2発生源としてドライアイスを使用して密閉容器で適度な圧力を達成します。

Herein is presented a general strategy to perform reactions under mild to moderate CO2 pressures with dry ice. This technique obviates the need for ...

CO2 Photoreduction to CH4 Performance Under Concentrating Solar Light

We demonstrate a method for the enhancement of CO2 photoreduction. As the driving force of a photocatalytic reaction is from solar light, the basic idea is to use concentration technology to raise the incident solar light intensity. Concentrating a large-area light onto a small area cannot only increase light intensity, but also reduce the catalyst amount, as well as the reactor volume, and increase the surface temperature. The concentration of light can be realized by different devices. In this manuscript, it is realized by a Fresnel lens. The light penetrates the lens and is concentrated on a disc-shaped catalyst. The results show that both the reaction rate and the total yield are efficiently increased. The method can be applied to most CO2 photoreduction catalysts, as well as to similar reactions with a low reaction rate at natural 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 technology.

CO 2 太陽光集中下でのCH4性能へのCO2光減少

We demonstrate a method for the enhancement of CO2 photoreduction. As the driving force of a photocatalytic reaction is from solar light, the basic idea ...

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

A significant number of heterogeneously-catalyzed chemical processes occur under liquid conditions, but simulating catalyst function under such conditions is challenging when it is necessary to include the solvent molecules. The bond breaking and forming processes modeled in these systems necessitate the use of quantum chemical methods. Since molecules in the liquid phase are under constant thermal motion, simulations must also include configurational sampling. This means that multiple configurations of liquid molecules must be simulated for each catalytic species of interest. The goal of the protocol presented here is to generate and sample trajectories of configurations of liquid water molecules around catalytic species on flat transition metal surfaces in a way that balances chemical accuracy with computational expense. Specifically, force field molecular dynamics (FFMD) simulations are used to generate configurations of liquid molecules that can subsequently be used in quantum mechanics-based methods such as density functional theory or ab initio molecular dynamics. To illustrate this, in this manuscript, the protocol is used for catalytic intermediates that could be involved in the pathway for the decomposition of glycerol (C3H8O3). The structures that are generated using FFMD are modeled in DFT in order to estimate the enthalpies of solvation of the catalytic species and to identify how H2O molecules participate in catalytic decompositions.

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 methods.

密度汎関数理論と力場分子動力学を用いた異種水/金属触媒インタ フェースのマルチ サンプリング

A significant number of heterogeneously-catalyzed chemical processes occur under liquid conditions, but simulating catalyst function under such conditions ...

Tuning the Acidity of Pt/ CNTs Catalysts for Hydrodeoxygenation of Diphenyl Ether

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid nanosheets, a series of Pt/xHMNO6/CNTs with different solid acid compositions (x = 5, 20 wt%; M = Nb, Ta; N = Mo, W) have been prepared by carbon nanotube pretreatment, protonic exchange, solid acid exfoliation, aggregation and finally Pt particles impregnation. The Pt/xHMNO6/CNTs are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and NH3-temperature programmed desorption. The study revealed that HNbWO6 nanosheets were attached on CNTs, with some edges of the nanosheets being bent in shape. The acid strength of the supported Pt catalysts increases in the following order: Pt/CNTs &#60; Pt/5HNbWO6/CNTs &#60; Pt/20HNbMoO6/CNTs &#60; Pt/20HNbWO6/CNTs &#60; Pt/20HTaWO6/CNTs. In addition, the catalytic hydroconversion of lignin-derived model compound: diphenyl ether using the synthesized Pt/20HNbWO6 catalyst has been investigated.

A protocol for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs is presented.

ジフェニルエーテルのヒドロデオキシゲーションのためのPt/CNT触媒の酸性度のチューニング

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid ...

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 infrared spectroscopy is an inexpensive, highly sensitive, and selective valuable tool to investigate the interaction of polycrystalline solids with adsorbates. Vibrational spectra provide information on the chemical nature of adsorbed species and their structure. Thus, they are very useful for obtaining molecular level understanding of surface species. The IR spectrum of the sample itself gives some direct information about the material. General conclusions can be drawn concerning hydroxyl groups, some stable surface species and impurities. However, the spectrum of the sample is &#34;blind&#34; with respect to the presence of coordinatively unsaturated ions and gives rather poor information about the acidity of surface hydroxyls, species decisive for the adsorption and catalytic properties of the materials. Furthermore, no discrimination between bulk and surface species can be made. These problems are solved by the use of probe molecules, substances that interact specifically with the surface; the alteration of some spectral features of these molecules as a result of adsorption provides valuable information about the nature, properties, location, concentration, etc., of the surface sites.
The experimental protocol for in-situ IR studies of gas/sample interaction includes preparation of a sample pellet, activation of the material, initial spectral characterization through the analysis of the background spectra, characterization by probe molecules, and study of the interaction with a particular set of gas mixtures. In this paper we investigate a zirconium terephthalate metal organic framework, Zr6O4(OH)4(BDC)6 (BDC = benzene-1,4-dicarboxylate), namely UiO-66 (UiO refers to University of Oslo). The acid sites of the UiO-66 sample are determined by using CO and CD3CN as molecular probes. Furthermore, we have demonstrated that CO2 is adsorbed on basic sites exposed on dehydroxylated UiO-66. Introduction of water to the system produces hydroxyl groups acting as additional CO2 adsorption sites. As a result, CO2 adsorption capacity of the sample is strongly enhanced.

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 discussed.

イン・シチュガス・固体相互作用の調査ツールとしてのFTIR分光法:UiO-66金属有機フレームワークにおける水強化CO2吸着

In situ infrared spectroscopy is an inexpensive, highly sensitive, and selective valuable tool to investigate the interaction of polycrystalline solids ...

モリブデンカーバイド触媒上の酢酸の昇温脱酸素化

要約

さらに動画を探す

この動画の章

エアロゾルによる金属酸化物の構造の化学蒸着: 酸化亜鉛棒

同時マルチ表面 Anodizations、階段のような逆バイアスで硫酸陽極酸化アルミニウムとシュウ酸電解質の剥離

合成と電気化学的 CO₂削減のため単一原子の遷移金属触媒の性能評価

二酸化バナジウムと温度依存性の光学モデルの原子層堆積法

ミル-96、UiO-66-NH₂原子層のソルボサーマル合成繊維のマット上金属酸化皮膜に堆積

固体 CO₂発生源としてドライアイスを使用して密閉容器で適度な圧力を達成します。

CO 2 太陽光集中下で_のCH4性能へのCO2光減少

密度汎関数理論と力場分子動力学を用いた異種水/金属触媒インタフェースのマルチサンプリング

ジフェニルエーテルのヒドロデオキシゲーションのためのPt/CNT触媒の酸性度のチューニング

イン・シチュガス・固体相互作用の調査ツールとしてのFTIR分光法:UiO-66金属有機フレームワークにおける水強化_CO2吸着

モリブデンカーバイド触媒上の酢酸の昇温脱酸素化

要約

さらに動画を探す

この動画の章

エアロゾルによる金属酸化物の構造の化学蒸着: 酸化亜鉛棒

同時マルチ表面 Anodizations、階段のような逆バイアスで硫酸陽極酸化アルミニウムとシュウ酸電解質の剥離

合成と電気化学的 CO2削減のため単一原子の遷移金属触媒の性能評価

二酸化バナジウムと温度依存性の光学モデルの原子層堆積法

ミル-96、UiO-66-NH2原子層のソルボサーマル合成繊維のマット上金属酸化皮膜に堆積

固体 CO2発生源としてドライアイスを使用して密閉容器で適度な圧力を達成します。

CO 2 太陽光集中下でのCH4性能へのCO2光減少

密度汎関数理論と力場分子動力学を用いた異種水/金属触媒インタ フェースのマルチ サンプリング

ジフェニルエーテルのヒドロデオキシゲーションのためのPt/CNT触媒の酸性度のチューニング

イン・シチュガス・固体相互作用の調査ツールとしてのFTIR分光法:UiO-66金属有機フレームワークにおける水強化CO2吸着

合成と電気化学的 CO₂削減のため単一原子の遷移金属触媒の性能評価

ミル-96、UiO-66-NH₂原子層のソルボサーマル合成繊維のマット上金属酸化皮膜に堆積

固体 CO₂発生源としてドライアイスを使用して密閉容器で適度な圧力を達成します。

CO 2 太陽光集中下で_のCH4性能へのCO2光減少

密度汎関数理論と力場分子動力学を用いた異種水/金属触媒インタフェースのマルチサンプリング

イン・シチュガス・固体相互作用の調査ツールとしてのFTIR分光法:UiO-66金属有機フレームワークにおける水強化_CO2吸着