Monitoring Catalytic reactions on Nanoparticles by solid state NMR: a joint experimental and theoretical approach

通过固态核磁共振监测纳米颗粒的催化反应：一种联合实验和理论方法

• 批准号: 208520256
• 负责人: Professor Dr. Gerd Buntkowsky
• 金额: --
• 依托单位: Laboratoire de Physique et Chimie des Nanoobjets (UMR5215-IRSAMC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2015-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/208520256?language=en
• 关键词: Monitoring; Catalytic; reactions; Nanoparticles; solid

The project aims at studying the surface reactivity of metal nanoparticles (Ru, Pd, Au, RuCu) prepared from organometallic precursors and accommodating or not ancillary ligands (phosphines and N-heterocyclic carbenes) towards representative catalytic reactions, namely i) CO oxidation as a well-documented example, ii) arene hydrogenation for colloidal catalysis and iii) Fischer- Tropsch synthesis (FTS) for large scale heterogeneous catalysis. The course of the reactions will be monitored by various NMR experiments. Gas phase NMR, associated with mass spectrometry, will be used to characterize the course of reactions and the products in cases i) and iii) whereas solution NMR (including DOSY) will be used in case ii). The surface species, their location and dynamics will be characterized by solid state NMR. More precisely, surface deuterides location and dynamics will be achieved by temperature dependant static solid state NMR. 13CO will be used as a probe molecule to locate ancillary ligands, to determine directly or by selectively poisoning the reactions sites and to monitor the reactivity of the particles towards CO oxidation and Fischer-Tropsch Synthesis. For this purpose, variable temperature 13C MAS-NMR spectroscopy will be used. These experiments will be carried out in close interaction with a theoretical approach using DFT methods to locate the ligands and determine the reactions pathways on realistic models (Ru55). This will help both to validate experimental results (for example deuterium location) and understand the behavior of the adsorbates in order to propose a model of the catalytic reactions.

该项目旨在研究由有机金属前体和容纳或不容纳辅助配体（膦和N-杂环卡宾）制备的金属纳米颗粒（Ru，Pd，Au，RuCu）对代表性催化反应的表面反应性，即i）CO氧化作为一个有据可查的例子，ii）用于胶体催化的芳烃氢化和iii）用于大规模多相催化的费托合成（FTS）。反应过程将通过各种NMR实验进行监测。与质谱法相关的气相NMR将用于表征情况i）和iii）中的反应过程和产物，而溶液NMR（包括DOSY）将用于情况ii）。表面物种，它们的位置和动力学将通过固态NMR表征。更准确地说，表面氘化物的位置和动力学将通过温度依赖的静态固态NMR来实现。13 CO将被用作探针分子来定位辅助配体，以直接或通过选择性毒化反应位点来确定，并监测颗粒对CO氧化和费托合成的反应性。为此，将使用变温13 C MAS-NMR光谱法。这些实验将与理论方法密切互动，使用DFT方法定位配体并确定现实模型（Ru 55）上的反应途径。这将有助于验证实验结果（例如氘位置）和了解吸附物的行为，以便提出催化反应的模型。

项目成果

Secondary phosphine oxides as pre-ligands for nanoparticle stabilization

• DOI: 10.1039/c2cy20683h
• 发表时间: 2013-02
• 期刊: Catalysis Science & Technology
• 影响因子: 5
• 作者: E. Rafter;T. Gutmann;F. Löw;G. Buntkowsky;K. Philippot;B. Chaudret;P. V. Leeuwen

Tin-decorated ruthenium nanoparticles: a way to tune selectivity in hydrogenation reaction.

• DOI: 10.1039/c4nr00791c
• 发表时间: 2014-07
• 期刊: Nanoscale
• 影响因子: 6.7
• 作者: E. Bonnefille;F. Novio;T. Gutmann;R. Poteau;P. Lecante;J. Jumas;K. Philippot;B. Chaudret

From molecular complexes to complex metallic nanostructures--2H solid-state NMR studies of ruthenium-containing hydrogenation catalysts.

• DOI: 10.1002/cphc.201300200
• 发表时间: 2013-09
• 期刊: Chemphyschem : a European journal of chemical physics and physical chemistry
• 作者: T. Gutmann;I. del Rosal;B. Chaudret;R. Poteau;H. Limbach;G. Buntkowsky

Investigation of the surface chemistry of phosphine-stabilized ruthenium nanoparticles--an advanced solid-state NMR study.

• DOI: 10.1039/c3cp52927d
• 发表时间: 2013-09
• 期刊: Physical chemistry chemical physics : PCCP
• 作者: T. Gutmann;E. Bonnefille;H. Breitzke;P. Debouttière;K. Philippot;R. Poteau;G. Buntkowsky;B. Chaudret