Novel synthesis method and science based tuning of mesoporous graphitic carbons as catalysts for oxidative dehydrogenation of alcohols

介孔石墨碳作为醇氧化脱氢催化剂的新合成方法和基于科学的调整

• 批准号: 323078467
• 负责人: Professor Dr.-Ing. Bastian Etzold
• 金额: --
• 依托单位: Institute of Metals Research
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/323078467?language=en
• 关键词: Novel; synthesis; method; science; based

Catalytic materials are key components in chemical industry. As game changing technology development of novel catalytic system is crucial for reducing the environmental footprint. In the past two decades solely carbon based materials could be introduced as a new class of catalysts. Especially nanocarbons were investigated in the oxidative dehydrogenation of ethylbenzene or chain alkanes, where attractive yields and selectivity were achieved. Nevertheless, for an industrial application such nano-materials keep some drawbacks with regard to the scale up of their synthesis, the pressure drop induced by a fix bed of nanomaterials and unclear health risks. Thus replacing currently employed carbon nano-materials as catalyst is of interest. Using carbide-derived model carbons we could recently demonstrate that novel porous carbon powders show equivalent catalytic performance as nanocarbons. In addition, these materials show handling properties like normal activated carbon powders. In preliminary work for this proposal we could demonstrate that mesoporous and graphitic carbons could also be synthesised more sustainable by vacuum annealing of activated carbons (AC). These AC can stem from sources like wood, coconut, peat or agriculture wastes and would be a more ecological way to produced the desired carbons. To allow a catalyst tuning through the new synthesis method it is envisaged to deduce the influence of the precursor properties, vacuum annealing conditions and graphitization catalysts on the resulting material properties.The project will not stop with development of the novel synthesis method for AC derived mesoporous graphitic carbons, but also employ and optimize these materials for the oxidative dehydrogenation of alcohols to aldehydes. As the use of fossil oil and gas in chemical industry is in future problematic due to the peak oil and greenhouse gas problem, one of the utmost challenges of chemical industry is the transition towards sustainable feedstock. Here future important platform chemicals can be alcohols, as they can be produced sustainable (e.g. ethanol and butanol by fermentation). In this sense obtaining aldehydes from ODH of these alcohols could lead directly to important intermediates for chemical industry. Furthermore, the studied carbon materials shall replace classical dehydrogenation catalysts like noble metals or metal oxides. From the few reports available carbon catalysts could achieve high selectivity or operate at milder process conditions, which makes them an attractive alternative. For the materials optimization in this catalytic application, we want to fundamentally understand coupled alcohol substrate and carbon material influence on the catalytic performance. In this sense, the material synthesis, characterization, catalytic experiments and deducing the catalytic mechanisms will go hand in hand. This gets possible through the German-Chinese collaboration allowing to combine the needed knowledge and methodologies.

催化材料是化学工业的关键部件。新型催化体系的开发对于减少环境足迹至关重要。在过去的二十年里，只有碳基材料才能作为一种新型催化剂被引入。特别是在乙苯或链烷烃的氧化脱氢反应中，纳米碳得到了很好的收率和选择性。然而，对于工业应用而言，这些纳米材料在合成规模扩大、纳米材料固定床引起的压降以及不清楚的健康风险方面存在一些缺点。因此，取代目前使用的碳纳米材料作为催化剂是人们感兴趣的。利用碳化物衍生的模型碳，我们最近可以证明新型多孔碳粉具有与纳米碳相当的催化性能。此外，这些材料表现出与普通活性炭粉末一样的处理性能。在本提案的初步工作中，我们可以证明，通过活性炭（AC）的真空退火，介孔碳和石墨碳也可以更可持续地合成。这些交流电可以来自木材、椰子、泥炭或农业废物等来源，是一种更生态的方式来生产所需的碳。为了通过新的合成方法调整催化剂，设想推导前驱体性质、真空退火条件和石墨化催化剂对所得材料性质的影响。该项目不会停止开发新的合成方法的AC衍生介孔石墨碳，但也使用和优化这些材料的醇氧化脱氢制醛。由于石油峰值和温室气体问题，化石石油和天然气在化学工业中的使用在未来是有问题的，化学工业面临的最大挑战之一是向可持续原料过渡。在这里，未来重要的平台化学品可能是醇，因为它们可以可持续地生产（例如通过发酵生产乙醇和丁醇）。从这个意义上说，从这些醇的ODH中获得醛可以直接导致化学工业的重要中间体。此外，所研究的碳材料将取代传统的脱氢催化剂，如贵金属或金属氧化物。从少数报道中，可用的碳催化剂可以实现高选择性或在较温和的工艺条件下运行，这使它们成为一个有吸引力的替代品。对于该催化应用中的材料优化，我们希望从根本上了解耦合的醇底物和碳材料对催化性能的影响。从这个意义上说，材料的合成、表征、催化实验和催化机理的推导将齐头并进。这是通过中德合作实现的，可以将所需的知识和方法结合起来。

项目成果

Oxygen assisted butanol conversion on bifunctional carbon nanotube catalysts: Activity of oxygen functionalities

• DOI: 10.1016/j.carbon.2020.08.053
• 发表时间: 2020-12-01
• 期刊: CARBON
• 影响因子: 10.9
• 作者: Li, Fan;Yan, Pengqiang;Qi, Wei
• 通讯作者: Qi, Wei

Methodology for the identification of carbonyl absorption maxima of carbon surface oxides in DRIFT spectra

• DOI: 10.1016/j.cartre.2020.100020
• 发表时间: 2021-04
• 作者: Felix Herold;Oliver Leubner;Katharina Jeschonek;C. Hess;A. Drochner;W. Qi;B. Etzold

Methanol conversion on borocarbonitride catalysts: Identification and quantification of active sites

硼碳氮化物催化剂上的甲醇转化：活性位点的识别和定量

• DOI: 10.1126/sciadv.aba5778
• 发表时间: 2020-06
• 期刊: Science Advances
• 影响因子: 13.6
• 作者: Zhang Xuefei;Yan Pengqiang;Xu Junkang;Li Fan;Herold Felix;Etzold Bastian J. M.;Wang Peng;Su Dang Sheng;Lin Sen;Qi Wei;Xie Zailai
• 通讯作者: Xie Zailai

Synthesis strategies towards amorphous porous carbons with selective oxygen functionalization for the application as reference material

• DOI: 10.1016/j.carbon.2020.09.030
• 发表时间: 2021-01-01
• 期刊: CARBON
• 影响因子: 10.9
• 作者: Herold, Felix;Leubner, Oliver;Etzold, Bastian J. M.
• 通讯作者: Etzold, Bastian J. M.

Methanol oxidative dehydrogenation and dehydration on carbon nanotubes: active sites and basic reaction kinetics

• DOI: 10.1039/d0cy00619j
• 发表时间: 2020-08
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: Pengqiang Yan;Xuefei Zhang;Felix Herold;Fan Li;Xueyan Dai;Tianlong Cao;B. Etzold;W. Qi