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注意:操作之前使用的所有化学品，请咨询安全数据表（SDS）。如果用空气或氧气和点火源相结合的易燃气体可能存在爆炸的危险。氢气是一种极易燃的气体。酸是腐蚀性的，并且在皮肤或眼睛接触的情况下，有刺激性，并可能产生灼伤。乙酸是一种易燃液体和蒸气，因此可点燃和/或明火，火星和氧化剂的存在下发生爆炸，除了可能造成严重的皮肤灼伤和眼损伤。当未在封闭系统或容器，乙酸应化学通风柜的内部处理。纳米材料催化剂的危害没有得到很好的理解，因此这些材料应内部的局部排风罩（ 即化学罩），以减少暴露进行处理。个人防护装备（安全眼镜，丁腈手套，实验室外套，封闭趾鞋，裤长），而处理这些材料，应佩戴。注:在本工作中使用的四极质谱仪（MS）配备有一个法拉第杯检测器，并在70伏特的电离能量工作。对所有的反应产物定量，微型气相色谱仪（μGC）包括总共四个各配备有热导检测器（TCD）的独立的列。对于列类型指的是具体的设备/材料清单。清洁的气体过滤器是在μGC载体气体（他中，Ar）用于防止柱降解由于H 2 O，以及改善的热导率检测器的性能。简言之，μGC单元通常更便宜，具有比常规的气相色谱仪系统的采样时间较短，但是这可以被分析（ 例如 ，最有效的永久气体，短链烃和低分子量的含氧化合物）的化合物中被限制和被限制热导检测器。 1. SY准备干<ol><li> 设备启动 <ol><li>验证MS和μGC被供电上，稳定的，调谐和μGC被校准。用于MS和μGC的调谐和方法的开发，指的是分析设备的操作手册。对于μGC校准的详细过程在其他地方出版了17，18，19，20，21，和这里使用的特定校准过程概述在下面的说明中。 注:化合物是通过与已知标准的保留时间比较确定。定量分析进行了使用的TCD120，这是校准，已知浓度的标准。简要地说，各气标准送入到μGC用两级调节器和浓度被允许稳定。一旦气体浓度稳定-d作为由稳定在色谱峰面积证实，采取了标定气体标准中的至少三个样品。重复对所有相关标准气的过程。从峰面积的最佳拟合的从一式三份的校准样品的线作为已知的气体标准浓度的函数生成针对每个种类的响应因子。所需的校准在实验中观察到的物种和浓度范围，并且因此，在表1中进行了概述。在一般情况下，对于每个物种最少三个校准点，跨越整个预期范围，是优选的。对于相对不挥发（ 即 ，低蒸汽压）物种如乙酸，获得具有适当浓度的气体校准标准可能是困难的，因此，单点校准可能是唯一的选择。 </li><li>以防止气相反应物和产物中的系统的行缩合，确保从系统线反应器到MS，并且从MS到μGC加热至84℃和105℃，分别使用绝缘热带（ 图1A）和一个热胶带温度控制器。这些温度都基于反应物和产物种类，制造商的规格为供给至μGC气体的最高允许温度，并且需要保持足够低的MS真空压力的沸点选择。 注:所有系统行316 / 316L不锈钢，除非另有说明。录像机和压缩式接头专门用于整个系统，以在反应器的热电偶一个例外。石英"U形管"反应器连接到系统油管配件是录像机;然而，超乇件也将是在这项工作中使用的条件下适用。这样的嵌合被用于反​​应器的热电偶，在具有无聊通联合一起，允许热电偶T的位置Ø进行调整。乙酸兼容O形环（全氟）用于该嵌合。 </li><li>使用低真空泵以减少低于1×10的MS压力-4托。 </li><li>电源涡轮真空泵用于MS和允许真空泵足够的时间来达到所希望的真空压力（&lt;1×10 -7乇）。 </li><li>填充饱和（ 图1B）与冰醋酸以适当的通风橱。 <ol><li>小心倒入乙酸进入饱和器;最小化的酸和将用于完成与铜垫圈嵌合的不锈钢"刀刃"之间的接触。 </li><li>放置在饱和器单元的底部一半的铜垫片，并对齐饱和的上半部在适当位置。 </li><li>通过凸缘孔插入螺栓，并用手拧紧入垫圈。用扳手进一步拧紧螺栓，在每个半圈交替的螺栓，以确保统一的密封ACROSS中的铜垫片。 </li></ol></li><li>安装TPRxn系统上饱和。 注:当安装饱和，保证了饱和的方向是正确的。氦应流经不锈钢管进液的乙酸，与蒸汽通过顶部空间离开饱和器。安装不当可能会导致液体乙酸进入系统线路。 </li></ol></li><li> 电抗器加载 <ol><li>从储存/干燥炉（名义上保持在110-150℃）除去一个洁净，干燥，石英"U形管"反应器（ 图2）。 </li><li>一旦反应器已经冷却至室温，装入石英棉少量到反应器中。使用支持催化剂床所需的石英棉的最小量。 </li><li>使用干净的，僵硬的，金属丝密封杆（ 如 3/32"OD，316 / 316L不锈钢），轻轻石英管推羊毛下来直段邻结束F中的管。 </li><li>称量50mg的催化剂，并用200毫克石英碎片混合以防止窜并确保通过催化剂床温度一致。使用，筛的石英芯片的粒度类似（ 即 ，180-300微米），以该催化剂的前（ 即 ，150-250微米），以限制物理混合物的不均匀性。 注:筛分石英碎片到一个较小的粒径会导致穿过催化剂床的较大的压力降。 </li><li>用称量纸和清洁液漏斗倾催化剂/石英芯片混合物到反应器中，使得催化剂床就座于石英棉载体的顶部。 </li><li>轻轻地推在催化剂床的顶部的第二小块石英棉代替固定催化剂床。 </li></ol></li><li> 电抗器安装 <ol><li>用丙酮清洗器热电偶去除先前实验的残留物。 </li><li>通过第一连接和TIG安装反应堆htening嵌合在催化剂床的上游侧（ 即 ，石英反应器管的直线部分）。 </li><li>连接并拧紧在催化剂床的下游侧的嵌合。在这里演示系统中使用这种灵活的装配不锈钢管的短款减轻反应器安装和拆卸过程中微妙的"U型管"反应堆潜力休息。 </li><li>通过一个无聊通嵌合推热电偶，使得热电偶的前端坐落在催化剂床的顶部边缘调整反应器中的热电偶的位置。热电偶应通过位于催化剂床的顶部的石英棉推动。 注:全氟弹性体（FFKM）O形环与反应物和产物存在于本实验兼容，因此建议用于密封接头。 </li><li>小心抬起炉（ 图1C）的最高水平的"U-TU允许是"反应器中，使得该炉不接触反应器的顶部边缘。不允许在反应器的底部以接触炉的底部。 </li><li>裹有绝缘炉子上方的"U形管"反应器的暴露部分。 </li></ol></li></ol> 2.反应堆启动<ol><li> 惰性清洗 注意:该反应器系统和分析设备必须排放到安全的位置，如通风橱使人们和其它实验室设备不暴露于有害的气体和蒸气。开始之前的任何气体的流量，相应的压缩气瓶和两级调节器输送阀应打开。如果需要的话，该调节器输送压力应调节至在该相关联的质量流量控制器（MFC）被校准的入口压力。从微生物燃料电池的排出压力不应超过140千帕，在μGC的入口由所允许的最大压力限定的极限。 <ol><li&gt;打开超高纯度（UHP）他的MFC和反应器之间的截止阀（该阀是本以防止回流到他MFC），保证了三通阀是路由气体从反应器中至局部排风线（ 图3）。 注意:除非另有规定，所有的压力给出了相对于本地大气压力（表压）。水器到每个气体进料管线的添加，建议从气体除去任何痕量的水。 </li><li>通过校准的MFC的流超高压He气在40标准立方厘米每分钟（sccm）的。该流量已经凭经验确定以有效地清除在合理的时间框架（ 约 45-60分钟）内的空气和残余气体的系统。 注:阀门已被放置在微生物燃料电池的立即下游，以防止残余的乙酸蒸气，这可能会导致对微生物燃料电池损坏回流。当原料气体流，它通过启动流动是很重要的微生物燃料电池立即打开这些系统线路阀后。 </li><li>验证系统压力没有上升到超过7千帕。 注:较高的系统压力可以指示阀是封闭的或穿过催化剂床的压降是高于可接受。如果是后者，增加的石英碎片与催化剂混合的量可以减少穿过催化剂床的压降。 </li><li>使用与MS相关联的计算机软件，启动联机的MS。设置在MS从质量 - 电荷（M / Z）扫描的0的比率为100。 注意:使用一扫描模式优选，因为它允许检测未知制品的使用选择性离子监测（SIM）模式。基于所述MS与以上0-100（M / Z）范围内的扫描局限性选择扫描范围通常为主要的乙酸的反应产物的分析就足够了。如果设备允许一个较大的范围内，扫描到102期望包括任何乙酸anhy的检测dride生产。 </li><li>打开MS气体取样口阀，以允许该MS系统的真空通过1微米孔画出的气体。 注:掺入录像机密封垫A 2微米的过滤器被安装只是1微米孔上游，以限制1微米孔的堵塞。 </li><li>通过打开入口和出口饱和阀，并随后关闭所述饱和器旁通阀从超高压他乙酸饱和吹扫空气。通过液体乙酸连续鼓泡表明系统线路阀在正确的位置，并且所述饱和器被安装在正确的流动取向。允许饱和，同时监测MS信号直到的 N 2和O 2（分别为M / Z = 28和32，）清除不再存在。 注意:如果它已在先前的实验中已经进行步骤2.1.6可以跳过。 </li><li>通过打开饱和旁通阀和关闭satur停止饱和吹扫员入口和出口阀。 </li><li>继续清除与UHP他的系统，直到他以外的所有M / Z信号（M / Z = 4）不再存在（可能因系统卷上需要45-60分钟）。 注:系统可能会保持在UHP他流，直到准备开始后续步骤。 </li></ol></li></ol> 3.催化剂预处理<ol><li> 原位氢气预处理 注意:在这一点上，该催化剂存在如钼的碳化物，并通过在别处公开的方法合成易地 。 9，22的原位包含氢预处理步骤以除去表面的氧（通常从氧气钝化以下合成所得），和/或除去有机配体可存在于催化剂表面作为合成的结果上。 <ol><li>继续在40 SCCM UHP他流。 </li><li>打开H 2罐钢瓶阀门。调整两如果需要的话，打开调节器针阀（见注2.1.1）级调节的输送压力。 </li><li>通过打开只是H 2的MFC下游的H 2系统线路切断阀和设置在MFC在1.3标准立方厘米流动开始的 H 2流。调整UHP他流动到36 SCCM。 注:3.5％ 的 H 2 / He气体混合物被选择为保持低于氢（4％）的爆炸下限的H 2 /他组合物。被选择37.3 SCCM的流量以达到给定的我们的系统中的微生物燃料电池的流量范围的限制所期望的混合组合物，以确保催化剂前处理过程中的H 2的稳定供应，并保持低于140千帕的系统压力。 </li><li>允许的H 2的气相浓度和他对，分别稳定（30-45分钟）通过监测MS信号M / Z = 4和2个对他和H 2。 </li><li>输入温度程序入炉控制器。一个典型的温度程序是小号如下:以5℃/分钟从室温至400℃的斜坡，在400℃保持2小时。 注:还原温度和保温时间往往取决于材料和经验来确定。在此基础上，碳化钼催化剂，这表明，当O 2去除H 2为H 2 O完成以前的程序升温还原研究，确定这些值。作为一个例子，对于大容量的斜方晶β钼2℃，将O 2去除率在400℃下完成以下2小时。以5℃的升温速度/分钟是足够慢以确保前处理是不破坏催化剂和足够快在合理的时间内完成。 </li><li>开始升温程序。 </li><li>在程序结束时，使反应器冷却至环境温度在流动的3.5％H 2 /他。 </li></ol></li></ol> 4.醋酸程序升温反应（TPRxn） <ol><li> 启动一个实验 <ol><li>继续在36和1.3标准立方厘米流速流入UHP他和H 2分别。 </li><li>通过打开入口和出口饱和阀，并随后关闭所述饱和器旁通阀开始乙酸蒸汽通过反应器的流动。 </li><li>路线气体流向μGC通过从当前位置切换该反应器下游的三通阀（从反应器到本地排气口发送气体）至μGC位置。 注:系统压力应开始增加。这个压力增加是由于通过在μGC单元中使用的1/16"管的压降，不应该被允许超过140千帕（此限制是基于在μGC的入口的最大允许压力）。 </li><li>允许乙酸的系统压力和气相浓度来稳定（需要取决于系统卷上60-90分钟）。 注意:醋酸交流编号浓度可以在MS通过从M / Z = 43和60系统压力可视化的实时数据进行跟踪通常稳定在约130千帕。 </li><li>程序炉内温度控制器以从室温变化至600℃以10℃/分钟。 注意:以10℃的升温速度/分钟是足够慢，以获得良好分辨的数据作为温度的函数，并且为了避免任何破坏的催化剂，但足够快以在合理的时间内完成的实验，并没有显着的催化剂失活。 </li><li>开始收集μGC样品尽可能经常。 注:此处使用的μGC方法允许采样一次5.5分钟。该MS数据应包括温度对时间数据和μGC数据应包括同步时间标记使得两个MS和μGC数据可以与温度相关。 </li><li>开始的温度程序启动μG后立即C示例。 </li></ol></li><li> 停止实验 <ol><li>当温度程序已完成，停止μGC序列。 </li><li>使用与MS相关联的计算机软件，把该MS关闭。 注:保持"上"在MS涡轮泵如果MS是在随后的实验中使用。 </li><li>关闭1微米MS节流阀。 </li><li>加载μGC方法设置列温度到其最大容许极限，如制造商推荐的。 注:运载气体到μGC必须保持。这种"烘烤"方法是由制造商推荐以除去由μGC列（清洁）氧，水和高沸点化合物。 </li><li>由H 2 MFC设置为0标准立方厘米和关闭的 H 2切断阀切断氢气流。 </li><li>允许将反应器冷却至环境温度，同时与以40sccm流动的超高压他吹扫该系统。 </li><li>当酷，关闭超高压他流动，并允许系统达到环境压力。 </li><li>一旦在环境压力下，路线气体使用三通阀的局部排气口。 </li></ol></li></ol> 5.反应堆卸<ol><li> 卸载反应堆 <ol><li>由他MFC设置为0 SCCM停止UHP他流。关闭位于紧接他MFC下游的超高压他线切断阀。 </li><li>松开超托热电偶接头和拉热电偶，并从催化剂床客场以方便拆除反应堆。 </li><li>通过首先断开嵌合在反应器的下游侧卸载反应器（ 即 ，连接到柔性不锈钢管接头）。 </li><li>断开在反应器的上游侧的嵌合。 </li><li>除去从系统和运输反应器中以化学通风柜。 </li></ol></li><li> 反应器清洗 <ol><li> Worki纳克在化学通风橱中，使用干净的，耐腐蚀金属丝（ 例如 ，24号镍铬丝）以除去一块石英棉上的催化剂床的顶部。 </li><li>倾用过的催化剂进入样品瓶保持在壳体反应后的表征期望在稍后的时间。 </li><li> 5.2.1，使用导线去除石英棉的剩余片。 </li><li>清洁用丙酮将反应器的内部。 注:一个管道清洁器可以与丙酮一起用于洗涤反应器的内侧，如果任何残留的碳的存在。 </li><li>在110℃下储存反应器在烘箱中以去除任何残留的水。如果烤箱不可用，该反应器可以用在化学通风橱压缩空气线吹入干燥并在干燥器中储存。 </li></ol></li></ol> 6.数据分析<ol><li> MS解卷积 注:MS解卷积的方法进行了简要这里列出。请参阅recenTLY发表的文献醋酸TPRxn MS数据的解卷积的完整摘要。 9，23 <ol><li>使用MS软件，下载个人米/ z比的数据作为反应温度的函数。 </li><li>适应由Zhang 等中使用的方法。 24，正确使用质量裂解模式的个别品种（见下面的讨论部分）重叠的MS信号。 </li><li>纠正类似于由柯描述的方法将卷积MS数据。等人 ，25岁 ，在电离效率的相对差异，四极的传输和电子倍增器的增益。 </li><li>使用归一化和校正数据，以获得关于催化剂性能的半定量信息。 </li></ol></li><li> μGC数据整合和分析 <ol><li>使用μGC软件，集成色谱峰。 </li><li>运用在1.1.1节中讨论的μGC校正生成的响应因子，改造峰面积计数为摩尔组成数据，观察每个物种。 </li><li>参考最近的文献为μGC数据分析过程的详细说明和定量信息也可以提供。 22 </li></ol></li></ol>

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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.

该TPRxn方法为催化材料的筛选的有力工具，提供关于催化剂作为反应温度的函数的活性和选择性的信息。其他程序升温方法如TPD，TPO和TPR可以提供反应物的吸附力，吸附位点的数量，和适当的催化剂的前处理过程的信息，但不提供直接的催化性能数据。要注意，在这一工作中详述的TPRxn方法不测量稳态的反应速率，因此，反应数据可包括催化剂稳定化，失活和运输限制的影响是重要的。然而，TPRxn?...

程序升温反应（TPRxn）是许多程序升温方法，包括解吸（TPD），氧化（TPO）和还原（TPR），并且进行经由催化剂与反应物的并发的曝光或随后在一个稳定增加1温度。 1，2，3 TPRxn是一个短暂的技术，该技术提供了有关催化剂的活性和选择性反应温度的函数的信息。 4，5，6，也是一个流行的技术:搜索文献亩产量达1000余源援引其使用关键字"程序升温反应&#39;的。 TPRxn实验在微反应器系统典型地执行的，配备有质谱仪（MS），用于将反应器流出物的实时分析和p的相关性erformance温度。反应气体可以通过质量流量控制器和液体可以通过注射泵或通过液体鼓泡惰性气体的蒸气被引入引入。该催化剂通常是在原位预处理以形成用于该反应所需的催化阶段。一些系统配有附加的分析设备，超出了典型质谱仪，以提供有关该催化剂选择性存在于催化剂中，或反应机理的定量或定性的信息，表面的种类。例如，变换原位傅立叶编程的温度红外光谱（FTIR）提供了有关表面物种具有不同反应温度演变信息。 7,8在这项工作中表现出的TPRxn系统配备除更典型的MS的气相色谱（GC）。这GC，配备了四个平行柱，使得更精确的量化反应产物的fication，但在分析频率所花费的产品通过柱以洗脱时间的限制。因此，MS和GC的组合可以是用于与反应物和产物的准确定量耦合实时识别特别有用。 这里，我们应用TPRxn方法来研究乙酸对碳化钼催化剂的脱氧。这是催化剂研究的一个有趣和重要的反应，醋酸是存在于生物质热解蒸气许多羧酸一个有用的模拟。 9在生物质热解蒸气的高氧含量就必须除氧以产生烃燃料，10，11，12和碳化钼催化剂显示有前途的许多生物质热解蒸气模型化合物，包括糠醛，1-丙醇脱氧性能，酚和乙酸。 9，13，14，15，16然而，在脱氧反应的碳化钼催化剂的活性和选择性取决于催化剂的结构和组成，反应物质和反应条件。 从乙酸TPRxn收集的数据表明，碳化钼催化剂活性为上述约脱氧反应300℃，并且当带催化剂的表征信息相结合允许经由乙酸流动率的计算温度的函数的催化剂活性的定量。该TPRxn结果表明，脱氧（ 即 ，CO键破）产品在温度低于约青睐400°C和脱羰基（ 即 ，CC键破）产品FAVO红色在温度高于约 400℃。此外，TPRxn研究示出了使用各种合成方法生产碳化钼催化剂在活动的变化和选择性（ 即 ，生产不同碳化钼催化剂的结构和组合物）。尽管如此，这些信息的值，并且更一般的TPRxn实验数据朝向催化剂设计和工艺优化的成功应用是所得到的数据的质量的函数。在整个过程TPRxn强调了潜在的困难和局限性慎重考虑和知识是至关重要的。

<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

程序升温反应（TPRxn）是在各种环境条件下筛分固体催化剂性能的一个简单而强大的工具。一个TPRxn系统包括一个反应器，炉，气体和蒸气源，流量控制，仪表量化的反应产物（ 例如 ，气相色谱仪），和仪器，以实时监控（ 例如 ，质谱仪）的反应。这里，我们应用TPRxn方法来研究碳化钼催化剂的乙酸，以及许多在生物质热解蒸气的升级/稳定的重要反应的脱氧。 TPRxn用于评估催化剂的活性和选择性，并测试假想反应途径（ 例如 ，脱羰基，ketonization，和氢化）。乙酸脱氧的TPRxn研究的结果表明，钼碳化物为在温度高于约该反应的活性催化剂300℃，并且反应主张脱氧（ 即 ，CO键破）产品在温度低于约 400°C和脱羰基（ 即 ，CC键破）产品在温度高于约 400℃。

在线MS提供了分析在实时将反应器出口的气体组合物中的能力。在线MS没有加上任何装置来分离分析前的产品，并且因此具有重叠质量裂解型态的化合物之间进行区分时，物种鉴定是具有挑战性。如表2所示，许多由乙酸TPRxn实验的共同产物的由多个共同M / Z信号特征。该MS数据的解卷积（M / Z = 1 - 100作为温度的函数）可用于向得到半定量数据，因为对于给定的?...

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

这里提出为微观尺度程序升温反应器用于在醋酸脱氧评估碳化钼的催化性能的操作的协议。

对碳化钼催化合成乙酸的程序升温脱氧

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

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11.4K 次观看.  National Renewable Energy Laboratory. 这里提出为微观尺度程序升温反应器用于在醋酸脱氧评估碳化钼的催化性能的操作的协议。 

视频: 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.

金属氧化物结构的气溶胶辅助化学气相沉积: 氧化锌棒

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

科研

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.

阳极氧化铝在硫酸和草酸电解质中的同时多表面 Anodizations 和阶梯式反向偏置剥离

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

工程学

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.

电化学 CO2还原的过渡金属单原子催化剂的合成及性能表征

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.

二氧化钒原子层沉积与温度依赖性光学模型

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.

溶剂热合成 MIL-96 和 UiO-66-NH2在纤维垫上原子层沉积金属氧化物涂层上的合成

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.

用干冰作为固体 CO2源实现密封容器中的适度压力

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光还原到 CH4在集中太阳光下的性能

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.

利用密度泛函理论和力场分子动力学对多相水-金属催化剂接口进行多尺度采样

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.

调整二苯醚氢氧化的Pt/CNT催化剂的酸度

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.

原位FTIR 光谱作为气体/固体相互作用研究工具:UiO-66 金属-有机框架中的水增强 CO2吸附

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

对碳化钼催化合成乙酸的程序升温脱氧

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金属氧化物结构的气溶胶辅助化学气相沉积: 氧化锌棒

阳极氧化铝在硫酸和草酸电解质中的同时多表面 Anodizations 和阶梯式反向偏置剥离

电化学 CO₂还原的过渡金属单原子催化剂的合成及性能表征

二氧化钒原子层沉积与温度依赖性光学模型

溶剂热合成 MIL-96 和 UiO-66-NH₂在纤维垫上原子层沉积金属氧化物涂层上的合成

用干冰作为固体 CO₂源实现密封容器中的适度压力

CO₂光还原到 CH₄在集中太阳光下的性能

利用密度泛函理论和力场分子动力学对多相水-金属催化剂接口进行多尺度采样

调整二苯醚氢氧化的Pt/CNT催化剂的酸度

原位FTIR 光谱作为气体/固体相互作用研究工具:UiO-66 金属-有机框架中的水增强 CO₂吸附