Project ANR- 12-IS08-01
 
Program Blanc International II – SIMI 8
 
Title: Microporous materials: green synthesis for green applications
 
Acronym: MicroGreen
 
Coordinator France: Dr. Valentin VALTCHEV (LCS, ENSICAEN – Université de Caen – CNRS)
 
Coordinator China: Prof. Teng BEN (Jilin University)
 

The present project deals with synthesis of microporous zeolite type materials with the ultimate goal to reach a deeper understanding of their mechanism of formation. Zeolites and zeolite-like materials are studied today and applied in many different ways and fields including but not limited to ion exchange, catalytic processes, adsorption applications, electronic and sensing applications as well as in medicine and nanotechnology. Zeolites are ecologically friendly and expanding the scope and range of their applications would improve and transform many technological and industrial processes towards more environmentally beneficial operations. Understanding the process of zeolite nucleation and crystal growth and the factors controlling the zeolite formation is of importance because it provides a basis for rational design and prediction of zeolite structures with desired properties, which include not only their crystal structure but also their physical and chemical properties such as size, shape stability, reactivity, and composition. Together with zeolites, metal-organic-frameworks (MOFs) and lately the porous aromatic frameworks (PAFs) attracted the attention of academic and applied scientists with their extremely high sorption capacity in respect to greenhouse gases.

A specific feature of proposed research is that the synthesis of zeolites (French team) and PAF-type materials (Chinese team) will be performed at ambient conditions. This approach will be used in order to slow down the crystallization kinetics and to study the intermediates under quasi in situ conditions. Thus detail information on the intermediates, type of structures, phases and inhomogeneities present at different stages of microporous materials formation and gel transformation will be obtained. This approach will also provide a fine control of crystal growth kinetics and thus synthesis of microporous phases that cannot be obtained under conventional conditions. Low temperature conditions will be further employed for synthesis of zeolites on supports that cannot withstand conventional hydrothermal treatment. Synthesized series of zeolites, PAFs and composites materials will be further used for greenhouse gases and water pollutants elimination.

The project includes:

1. development and optimization of synthesis techniques and their application to the synthesis of zeolites and PAFs crystals including conducting time-series synthesis experiments under variable conditions and starting materials in order to reveal the dynamics and kinetics as well as the spatial aspects of the process of transformation of the amorphous gels (suspensions) into crystalline solids;
2. structural and compositional characterization of the synthesis products and their intermediates;
3. iterative analysis of the results and modification of the experimental condition in order to achieve the set goals;
4. synthesis of zeolite-type materials under “green conditions” that includes minimum use of energy and full recycling of the reactants;
5. employment of these materials for gas phase (PAFs will be used) and liquid (zeolites will be used) separations addressing important environmental problems of modern society.

The project involves two groups that possess all critical and complementary expertise to address the tasks of the project in a rational and comprehensive way. The French team will concentrate its efforts on the preparation of classical zeolites, while the Chinese partner will work on recently discovered polymer aromatic framework molecular sieves. The parallel study of these two important groups of crystalline microporous materials will allow making parallels and distinguishing differences in the nucleation and crystal growth mechanism.

The number of participants and their implication in the project for the two partners are listed in the tables below:


LCS – France

JU – Changchun

Scientific meetings

The work on the project started in April, 2013. The coordination has been managed namely by E-mail and telephone discussions.
The first meeting was organized after 6 months work in Jilin University (Zhuhai campus), October 27-28, 2013. Thus after having already the experience of 6 months active work on the project the partners have had more in depth discussion and made a detail plan of the future work. A photograph from the first meeting is provided below.

Kick off meeting of French – China international project entitled “Microporous materials: green synthesis for green applications” (Abbreviation: MicroGreen)

France: Project ANR-12-IS08-01 / Program Blanc International II – SIMI 8

China: National Natural Science Foundation of China (Grant No. 21261130584)

Publications

French partner

• Inagaki, K. Thomas, V. Ruaux, G. Clet, T. Wakihara, S. Shinoda, S. Okamura, Y. Kubota, V. Valtchev

“Crystal Growth Kinetics as a Tool for Controlling the Catalytic Performance of a FAU-Type Basic Catalyst”

ACS Catalysis 2014, 4, 2333−2341

• Chen, T. Todorova, A. Vimont, V. Ruaux, Z. Qin, J.-P. Gilson, V. Valtchev

“In situ and post-synthesis control of physicochemical properties of FER-type crystals”

Microporous Mesoporous Materials 2014, in press (DOI:          10.1016/j.micromeso.2014.07.057)

China partner

• Lu, T. Ben, S. Xu, and S. Qiu

“Electrochemical Synthesis of a Microporous Conductive Polymer

Based on a Metal–Organic Framework Thin Film”

Angew. Chem. Int. Ed. 2014, 53, 6454 –6458

• Wu, J. Bai, Y. Jiang, G. Li, J. Huang, Y. Li, C. E. Anson, Annie K. Powell, and Shilun Qiu

“Rolling Up the Sheet: Constructing Metal−Organic Lamellae and

Nanotubes from a [{Mn3(propanediolato)2}(dicyanamide)2]n

Honeycomb Skeleton”

1. Am. Chem. Soc. 2013, 135, 18276−18279