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>
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The authors have nothing to disclose.

Die TPRxn Verfahren ist ein leistungsfähiges Werkzeug für das Screening von katalytischen Materialien, die Information über die Aktivität und Selektivität eines Katalysators als Funktion der Reaktionstemperatur. Andere temperaturprogrammierte Methoden wie TPD, TPO und TPR können Informationen über die Adsorptionsstärke von Reaktanden, die Anzahl von Adsorptionsstellen bereitzustellen und geeignete Katalysatorvorbehandlungsverfahren, aber keine direkte Daten katalytische Leistung. Es ist wichtig, dass die TPRxn M...

Temperaturprogrammierte Reaktion (TPRxn) ist eine von vielen temperaturprogrammierten Methoden, einschließlich Desorption (TPD), Oxidation (TPO) und Reduktion (TPR) und geht durch Einwirkung eines Katalysators auf einem Reaktanten gleichzeitig mit oder gefolgt von einer stetigen Zunahme Temperatur. 1, 2, 3 TPRxn ist eine transiente Technik , die Informationen über die Katalysatoraktivität und Selektivität als Funktion der Reaktionstemperatur zur Verfügung stellt. 4, 5, 6 Es ist auch eine beliebte Technik: Eine Suche in der &#39;Reaktionstemperatur programmiert &quot;Keywords in den Literaturausbeuten über 1.000 Quellen unter Berufung auf seine Verwendung. TPRxn Experimente werden typischerweise in einem Mikroreaktorsystem durchgeführt, mit einem Massenspektrometer ausgerüstet (MS) für die Echtzeitanalyse des Reaktoraustrags und Korrelation von performance mit der Temperatur. Reaktantengase können Massendurchflussregler und Flüssigkeiten eingeführt werden verwendet, kann durch Einblasen von Inertgas durch eine Flüssigkeit über eine Spritzenpumpe oder als Dampf eingebracht werden. Der Katalysator wird häufig in situ vorbehandelte die gewünschte katalytische Phase für die Reaktion zu bilden. Einige Systeme sind mit zusätzlichen Analysegeräten ausgestattet, über die typischen Massenspektrometer, quantitative oder qualitative Information über die Katalysatorselektivität bereitzustellen, Oberflächen vorhandenen Spezies auf dem Katalysator oder Reaktionsmechanismus. Beispielsweise die Temperatur in situ Fourier programmiert Transformations - Infrarotspektroskopie (FTIR) Informationen über die Entwicklung der Oberflächenspezies liefert mit der Reaktionstemperatur variiert. 7, 8 Das TPRxn System in dieser Arbeit demonstriert wird mit einem Gaschromatogramm (GC) zusätzlich zu den typischeren MS ausgestattet. Das GC, ausgestattet mit vier parallelen Spalten, ermöglicht eine genauere quantifizierung der Reaktionsprodukte, sondern wird in Analysefrequenz durch die Zeit, die die Produkte durch die Säulen zu eluieren nimmt beschränkt. Somit kann die Kombination von MS und GC als besonders nützlich für die Kopplung Echtzeitidentifikation mit genauen Quantifizierung der Reaktanten und Produkte. Hier wenden wir die TPRxn Methodik für die Desoxygenierung von Essigsäure auf Molybdäncarbid Katalysatoren zu untersuchen. Dies ist eine interessante und wichtige Reaktion in der Katalysatorforschung, wie Essigsäure ein nützliches analog für die vielen Carbonsäuren in Biomasse Pyrolysedämpfen ist. 9 Der hohe Sauerstoffgehalt in der Biomasse Pyrolysedämpfe Sauerstoffentfernung erforderlich Kohlenwasserstoffbrennstoffe zu erzeugen, 10, 11, 12 und Molybdäncarbid Katalysatoren Desoxygenierung Leistung gezeigt vielversprechend für viele Biomasse Pyrolyse Dampfmodellverbindungen, einschließlich Furfural, 1-Propanol,Phenole und Essigsäure. 9, 13, 14, 15, 16 ist jedoch die Aktivität und Selektivität der Katalysatoren in Molybdäncarbid Desoxygenierung Reaktionen in Abhängigkeit von der Katalysatorstruktur und der Zusammensetzung, die reagierenden Spezies und den Reaktionsbedingungen. Die Daten aus TPRxn Essigsäure gesammelt zeigt , dass Molybdäncarbid Katalysatoren für Desoxygenierungen oberhalb von ca. aktiv sind 300 ° C, und wenn sie mit Katalysatorcharakterisierungsinformationen ermöglicht die Quantifizierung der Katalysatoraktivität als Funktion der Temperatur über die Berechnung von Essigsäure Umsatzraten kombiniert. Die TPRxn Ergebnisse zeigen , dass Desoxygenierung (dh CO Bindungsbruch) Produkte bei Temperaturen unterhalb von ca. begünstigt werden 400 ° C und Decarbonylierung (dh CC Bindungsbruch) Produkte sind favorot bei Temperaturen über ca. 400 ° C. Zusätzlich können die Veränderungen in der Aktivität und Selektivität von Molybdäncarbid Katalysatoren unter Verwendung verschiedener Syntheseverfahren hergestellt ( das heißt, die Herstellung von verschiedenen Molybdäncarbid Katalysatorstrukturen und Zusammensetzungen) TPRxn Studien veranschaulichen. Dennoch erhalten der Wert dieser Informationen und, allgemeiner, die erfolgreiche Anwendung von TPRxn experimentellen Daten zu Katalysatordesign und Prozessoptimierung ist eine Funktion der Qualität der Daten. Die sorgfältige Abwägung und das Wissen über die möglichen Schwierigkeiten und Einschränkungen während des TPRxn Verfahren hervorgehoben ist von größter Bedeutung.

<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

Temperaturprogrammierte Reaktion (TPRxn) ist ein einfaches aber leistungsstarkes Werkzeug für das Screening von festen Katalysatorleistung bei einer Vielzahl von Bedingungen. A TPRxn System umfaßt einen Reaktor, Furnace-, Gas- und Dampfquellen, Flußsteuerung, Instrumentierung Reaktionsprodukte (beispielsweise Gaschromatographen) und Instrumentierung zur Überwachung der Reaktion in Echtzeit (beispielsweise Massenspektrometer) zu quantifizieren. Hier wenden wir die TPRxn Methodik Molybdäncarbid Katalysatoren für die Desoxygenierung von Essigsäure, eine wichtige Reaktion unter vielen in der Modernisierung / Stabilisierung von Biomasse Pyrolysedämpfe zu studieren. TPRxn wird verwendet , Katalysatoraktivität und Selektivität zu bewerten und hypothetischen Reaktionswege zu testen (zB Decarbonylierung, Ketonisierung, und Hydrierung). Die Ergebnisse der Studie TPRxn Essigsäure Desoxygenierung zeigen , dass Molybdäncarbid ein aktiver Katalysator für diese Reaktion bei Temperaturen oberhalb von ca. ist 300 ° C und die Reaktions BevorzugungenDesoxygenierung (dh CO Bindungsbruch) Produkte bei Temperaturen unter ca. 400 ° C und Decarbonylierung (dh CC Bindungsbruch) Produkte bei Temperaturen über ca. 400 ° C.

Die Online-MS bietet die Möglichkeit, die Gaszusammensetzung am Reaktorausgang in Echtzeit zu analysieren. Die Online-MS ist nicht mit einem Gerät gekoppelt Produkte vor der Analyse zu trennen, und somit zur Bestimmung von Arten ist eine Herausforderung, wenn die Muster zwischen den Verbindungen mit überlappenden Masse Fragmentierung zu unterscheiden. Wie in Tabelle 2 gezeigt, viele der üblichen Produkte aus Essigsäure TPRxn Experimente werden durch mehrere gemeinsa...

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

Hier vorgestellte ist ein Protokoll für den Betrieb eines Mikromaßstab temperaturprogrammierten Reaktor zur Auswertung der katalytischen Leistung von Molybdäncarbid während Essigsäure Desoxygenierung.

Temperaturprogrammierte Desoxygenierung von Essigsäure auf Molybdäncarbid Katalysatoren

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

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11.4K Aufrufe.  National Renewable Energy Laboratory.  Hier vorgestellte ist ein Protokoll für den Betrieb eines Mikromaßstab temperaturprogrammierten Reaktor zur Auswertung der katalytischen Leistung von Molybdäncarbid während Essigsäure Desoxygenierung. 

Serie: 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.

Aerosol-assisted Chemical Vapor Deposition von Metall-Oxid-Strukturen: Zinkoxid-Stangen

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

Forschung

Chemie

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.

Gleichzeitige Multi-Oberfläche Anodizations und Treppe-wie umgekehrte Vorurteile Ablösung der anodische Aluminium Oxide in Schwefelsäure und Oxalsäure-Elektrolyten

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

Ingenieurwesen

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.

Synthese und Performance Charakterisierungen von Übergangsmetall Einzelatom Katalysator für elektrochemische CO2 -Reduktion

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.

Atomic Layer Deposition von Vanadium Kohlendioxid und eine temperaturabhängige optische Modell

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.

Solvothermal Synthese von MIL-96 und UiO-66-NH2 auf atomarer Ebene hinterlegt Metall-Oxid-Beschichtungen auf Fasermatten

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.

Mäßiger Druck in verschlossenen Gefäßen, die Verwendung von Trockeneis als Solid CO2 zu erreichen

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.

CO2 Photoreduction zu 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 ...

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.

Multiskalen Sampling einer heterogenen Wasser/Metall Katalysator Schnittstelle mittels Dichtefunktionaltheorie und Kraftfeld Molecular Dynamics

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.

Optimierung der Säure von Pt/CNTs-Katalysatoren zur Hydrodeoxygenierung von Diphenylether

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.

In situ FTIR Spektroskopie als Werkzeug zur Untersuchung von Gas/Feststoff-Wechselwirkungen: Wasserverstärkte 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 ...

Temperaturprogrammierte Desoxygenierung von Essigsäure auf Molybdäncarbid Katalysatoren

Zusammenfassung

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Aerosol-assisted Chemical Vapor Deposition von Metall-Oxid-Strukturen: Zinkoxid-Stangen

Gleichzeitige Multi-Oberfläche Anodizations und Treppe-wie umgekehrte Vorurteile Ablösung der anodische Aluminium Oxide in Schwefelsäure und Oxalsäure-Elektrolyten

Synthese und Performance Charakterisierungen von Übergangsmetall Einzelatom Katalysator für elektrochemische CO₂ -Reduktion

Atomic Layer Deposition von Vanadium Kohlendioxid und eine temperaturabhängige optische Modell

Solvothermal Synthese von MIL-96 und UiO-66-NH₂ auf atomarer Ebene hinterlegt Metall-Oxid-Beschichtungen auf Fasermatten

Mäßiger Druck in verschlossenen Gefäßen, die Verwendung von Trockeneis als Solid CO₂ zu erreichen

CO₂ Photoreduction zu CH₄ Performance Under Concentrating Solar Light

Multiskalen Sampling einer heterogenen Wasser/Metall Katalysator Schnittstelle mittels Dichtefunktionaltheorie und Kraftfeld Molecular Dynamics

Optimierung der Säure von Pt/CNTs-Katalysatoren zur Hydrodeoxygenierung von Diphenylether

In situ FTIR Spektroskopie als Werkzeug zur Untersuchung von Gas/Feststoff-Wechselwirkungen: Wasserverstärkte CO2-Adsorption in UiO-66 Metal-Organic Framework