ALFA Programme Sub-programme B:
Scientific and Technical Training
INTERMEDIATE Technical Report
Contract Number: AML/19.0902/97/0666/II-0412-FA-FI Project Title: Design of NanoSorbents for Gas Storage Coordinating Institution: Université de Provence Network’s Name: NANOGASTOR
Study Area: CO2& CH4storage in nanoporous materials (zeolites, MOFs) Date of Signature: 21-03-2006
Date of coming into effect of the contract: 21-03-2006 Contract Duration: 3 years
Addenda (number and object):
Date of Contract Termination: 21-03-2009
Period covered by the INTERMEDIATE Report:
- from (Date of coming into effect of the contract): 15/05/2007
- to (Date of Contract Termination): 30/09/2008
Coordinator:
Full Name: Guillaume MAURIN Position: Lecturer
Faculty/Department/Service: Laboratoire MADIREL UMR CNRS 6121, Université de Provence (Marseille), Institut Gerhardt UMR CNRS 5253, Université Montpellier 2 (France).
Date: 05/11/2008 Signature:
Legal Representative:
Full name: Pr. Jean-Paul Caverni
Position: President of the Université de Provence
Date: Signature and stamp of the
Coordinating Institution:
Note: To be accepted, this report must be signed by the coordinator of the project and signed and stamped by the legal representative of the coordinating institution.
I. Introduction
Technical intermediate reports allow for comparative analysis of medium-term objectives and foreseen expected results with objectives and results really achieved during the period covered by the report.
The intermediate report appraisal will be a detailed compilation of the project activities and its implementation during the period covered by the report.
As regard to the form to be given to the present report, we recommend you to refer to the web page of the ALFA Programme (Cf. Guidelines for the Candidate, Annex II and FAQ, question n° 13):
“The Report will be constructed so that it permits a comparison between the objectives, means and results envisaged and those obtained or really applied.
To facilitate that comparison, we strongly recommend the presentation of a scheme made up of two columns: the first column intended for the objectives, activities and results envisaged; and the second column intended to indicate the degree of fulfilment of those objectives, activities and results.
Furthermore, it is essential to explain and justify all the cases of not accomplishment of the objectives, activities and results envisaged.
If an objective or result finishes being more successful than what it was envisaged, please inform us in detail about it as it will be of interest for the ALFA Programme and its beneficiaries.
II. Content
The Intermediate Technical Report will have to inform about the following elements:
II.1 Grant-holders mobility
Provide a final list of the grant-holders (you may use the model enclosed in the last page of this document with the following details: Name and address of grant-holder,
University/Faculty/Department of origin, host University/Faculty/Department, type of training, area of study, obtained diploma and length of the stay).
Provide us with the CVs of all grant-holders as well as with a list with all mobility flows occurred during the period.
Elements to consider:
- System used by the institution of origin for the open call for grants and system used for the selection of grant-holders, taking specially into account the key elements considered in the selection process and the kind of publication method used.
- Training Programme (s) used by the grant-holder (s).
- Language improvement courses. Identify the grant-holders who followed these courses and specify the conditions of the training;
- Conditions of the reception of the grant-holders (accommodation, health insurance, accidents, etc.)
- Application of agreements among the Network members for the exemption of inscription taxes as well as other charges requested by the institution of reception;
- Application of the agreements held by the Network so as to assure the return of the grant- holders to their institutions of origin, explaining in due case the conditions in which the return to the institution of origin took place;
- Application of agreements held by the Network in relation with the academic reconnaissance of the training activities by the institution of origin of the grant-holders and explaining the final result;
- Grades obtained by the grant-holders and whether the institute or origin or of reception awarded the grades.
- Actions taken by the tutors of the grant-holders in the institutions of reception, including meetings between the tutor and the responsible professor at the institution of origin.;
- Added value created by mobility for grant-holders, professors and other actors of the project, as well as for the institutions themselves.
II.2 Other activities
Inform about all ‘other activities’ developed by the network (besides mobility).
To describe the activities which have not been explained in a previous report, we strongly recommend to use a scheme made up of two columns: the first column intended for the objectives, activities and results envisaged in the contract; and the second column to indicate the degree of fulfilment of those objectives, activities and results. (Cf. Guidelines for the Candidate, Annex II and on the ALFA web page FAQ, question n° 13).
Indicate, for each activity not object of a previous progress report, the following:
- Type of activity (technical meetings, study visits, seminars, workshops, intensive courses, etc.); objectives envisaged; place and date of realisation;
- List of participants at the various activities; type of responsibility of the participants in their institution; nationality of the participants;
- Add, for each activity, all the products generated by the project (minutes of meetings, reports concerning the visits, etc.);
- Indicate if the activities have been developed along with or in parallel with other activities related or not to other ALFA projects;
- Indicate all results reached as regard to the planning and initial schedule;
- Comment the eventual difficulties met as part of the organisation;
III. Formal aspects
Intermediate Technical Reports must be drawn up in the language of the contract and must be accompanied by a Request for Payment (the model of the Request for Payment is Annex V of the contract).
They must be drawn up in duplicate (one original and one copy), at the latest two months after the period covered by the report.
The Intermediate Technical Report should be sent to the address mentioned in the Contract:
Payment requests, reports and changes in bank account details should be communicated to:
European Commission
EuropeAid – Co-operation Office To the Attention of the Financial Unit Office: J-54 6/24
B-1049-Brussels Belgium
Fax: + 32 2 295 69 77
Copies of the documents referred to above, and correspondence of any other nature, should be sent to:
European Commission
EuropeAid – Co-operation Office Unit B/2
ALFA Programme Office: J-54 4/29 B-1049-Brussels Belgium
Fax: + 32 2 299 10 80/47
As reminder, Intermediate Reports are made up of:
- Technical Report, - Financial Report,
- Audit Report, when stipulated in the particular conditions of the contract, - Request for payment (Annex V of the contract).
Do not forget to include the products generated by the project: publications, conclusions of meetings, books, CD ROM, etc as well as the Web page address.
Identification of Subprogram B Grant-Holders (Co-operation for Scientific and Technical Training) Project N°:
AML/19.0902/97/0666/II- 0412-FA-FI
Project Title: NANOGASTOR
Coordinating Institution: Université de Provence
Name of the network: Design of Nanosorbents for gas storage
Name of the Grant-holder
Institution and Department of origin
Institution and Department of
reception
N° of months
*Kind of training
**Gra de
Area of study (of the training)
Beginnin g of the training period
End of the training
period Name:
Last Name:
Contact: (tel., e-mail)
Institution:
Department:
Institution.:
Department:
Alvaro Sampieri Croda [email protected]
Universidad Nacional Autonoma de Mexico (UNAM)
Instituto de Investigaciones en Materiales
University College London Department
of Chemistry
12 AT Doctor
Structure Prediction of new nanoporous
materials
20-08-07 19-08-08
Sandra Loera [email protected]
Universidad Nacional Autonoma de Mexico (UNAM)
Instituto de Investigaciones en Materiales
Université de Provence Laboratoire Chimie
Provence
12 AT PhD
Adsorption of greenhouse gases in
MOFs materials using Microcalorimetry
01-10-07 30-09-08
Nilton Rosenbach [email protected]
Federal University of Rio de Janeiro
Institute of Chemistry
Université Montpellier 2 Institut C.Gerhardt UMR CNRS 5253
12 AT PhD
Modelling the adsorption performance of MIL materials with respect
to single or mixture of olefin gas
01-07-07 30-06-08
Alicia Sommer
Universidad Nacional Autonoma de Mexico (UNAM)
Instituto de Investigaciones en Materiales
CSIC Instituto de Ciencia
de Materiales de Madrid
6 AT Master
Synthesis of Pure
Silica Chabazite 01-10-07 30-03-08
Leslie Reguera-Nunez [email protected]
University of Havana Institute of Materials and
Reagents
Universidad Nacional Autonoma de Mexico (UNAM)
Instituto de Investigaciones en
Materiales
6 AT Ph.D
Study of the hydrogen storage in
Porous Molecular Materials from adsorption data and using spectroscopic
techniques
01-09-07 27-02-08
Luisa Marleny Rodríguez Albelo [email protected]
University of Havana Institute of Materials and
Reagents
University College London Department
of Chemistry
6 AT Ph.D
Synthesis, design and characterization of nanoporous metal – organic frameworks
(MOFs).
01-09-07 27-02-08
Inocente Rodriquez
[email protected] University of Havana Institute of Materials and
Reagents
CSIC Instituto de Ciencia
de Materiales de Madrid
1 RT Doctor
ITQ-12: towards a cheaper and safer
synthesis procedure 19-01-07 02-03-07
Rabdel Ruiz Salvador
[email protected] University of Havana Institute of Materials and
Reagents
Université Montpellier 2 Institut C.Gerhardt UMR CNRS 5253
1 RT Doctor
Diffusion of water in different cations exchanged chabazite
15-01-08 15-02-08
Yunier Garcia Balsabe [email protected]
University of Havana Institute of Materials and
Reagents
Université de Provence Laboratoire Chimie
Provence
6 AT Ph.D
Adsorption of carbon dioxide and hydrogen
in dealuminated zeolites and novel
MOF materials
15-10-08 15-04-08
Angel Rivera Ortega [email protected]
Universidad Nacional Autonoma de Mexico (UNAM)
Instituto de Investigaciones en Materiales
Université Montpellier 2 Institut C.Gerhardt UMR CNRS 5253
12 AT PhD
Experimental and theoretical exploration of the adsorption of various
vapours in MILs systems
01-10-08 30-09-08
Enrique Lima
Universidad Nacional Autonoma de Mexico (UNAM)
Instituto de Investigaciones en Materiales
University ofv
Leipzig 6 AT PhD
Investigation of the diffusion in nanoporous materials
using PFG NMR
01-12-08 30-05-09
TOTAL N° of grant-holders : 11 TOTAL N° of months: 80
Overview
This report includes the objectives and the degree of fulfilment of the activities scheduled by the NANOGASTOR program in the following areas: (i) research training mobility’s, (ii) meeting &
seminar (iii) scientific production and (iv) website during the period 15 May 2007- 30th September 2008
We provide for each successful student exchange realised during the first two Years of the project, the scientific report and the evaluation form in Annex. The CV’s of the students starting their mobility exchanges have been included as well as those of the candidates to the mobility’s, criteria for the election of the students participating in NANOGASTOR mobility’s are given.
The communication has operated smoothly between the NANOGASTOR members. Due to the difference in time zones, communications was mostly done through email and fax, although regular and express postal service was used when original documents were required. In some occasions telephone calls were required to clarify certain points or make final arrangements. In addition to the NANOGASTOR meetings, both EU and LA partners had the opportunity to meet at national and international conferences. The access to the web page was rather difficult from May this Year mostly due to internal technical problems in University College London (UCL) which was in charge to host it; the computer containing all the data of the website crashed and we were not able to recover the data. An updated version is now in progress with Dr. Dewi Lewis from UCL in collaboration with all the partners. Hopefullty, it will be accessible for end of the Year.
We remind that we encountered some problems to accomplish the advanced training mobility’s scheduled in the first year project. Following the recommendation given in the first Year meeting in Mexico, the student exchange was more fruitful during the second Year as described in the first part of this document. In addition we are attentive that a reasonable balanced male / female ratio of trainees is attained. Indeed, for the first 9 student exchanges, we have selected in close collaboration with each host group, 4 female and 5 male students. However, to fulfill the last open positions available for the 3rdYear, we will require an extension of the project for 8 months up to November 2009.
From a scientific point of view, as planned at the initial stage of the project, our scientific interest was to investigate and intelligently design nanoporous materials including zeolites and Metal Organic Framework materials most adapted for the storage of some specific gases such as hydrocarbon and carbon dioxide. Our consortium was built in order to be able to combine both modelling and experimental approaches by involving experts in the field of synthesis and experimental characterisation (adsorption, structure, diffusion), coupled with specialists in charge of the simulation. The training received by the students was of high quality which is very important for their future carrer in science. Each tutor paid attention to disseminate efficiently their work as attested by the large number of papers published in the best international journals of chemistry (Impact Factor higher than 3.5) provided in Annex. As a typical example, N. Rosenbach who spent 1 year in Montpellier reinforced his skills and applies now for a position of lecturer in Rio. In the same way, A.
Sampieri after his stay in London just got a permanent position in his country. The master student A.
Sommer after her stay in Madrid successfully started a PhD in Mexico. In that way, this second year has been very successful for all of the laboratories involved. This high quality research will be a strong starting point for the students who will start very soon their training in their respective host laboratories.
1. Research Training Mobility’s 1.1 Advanced training
1.1.1 Initial Objectives from EU to LA
1stYear 2ndYear
3 AT (6 months) 1 AT (12 months) Global: 30 months
4 AT (6 months) 1 AT (12 months) Global: 36 months
Total for the 2 first Years : 9 AT for a total duration of 66 months
Fulfilments of these positions
As previously mentioned in the first Year report, we faced some problems to fulfil all the mobility’s during the first year. However, the objectives proposed in the initial proposal for the two first years are realised:
Alvaro Sampieri : UNAM → UCL : 12 months (Annex 1)
Title: “Structure Prediction of new nanoporous materials”
Sandra Loera : UNAM → UP : 12 months (Annex Z)
Title: “Adsorption of greenhouse gases in MOFs materials using Microcalorimetry”
Nilton Rosenbach : UFRJ → UP-UM2 : 12 months (Annex 3)
Title: “Modelling adsorption and diffusion in SAPO and MAPO materials using both quantum and classical simulations”.
Alicia Sommer : UNAM → CSIC : 6 months (Annex 4) Title: “Synthesis of Pure Silica Chabazite”
Luisa Marleny Rodríguez Albelo : UH → UCL : 6 months (Annex 5)
Title: “ Synthesis, design and characterization of nanoporous metal – organic frameworks (MOFs).Synthesis of Pure Silica Chabazite”
Angel Rivera Ortega : UNAM → UM2 : 12 months (Annex 7)
Title: “Experimental and theoretical exploration of the adsorption of various vapours in MILs systems”
Yunier Garcia Balsabe : UH → UP : 6 months (Annex 8)
Title: “ Adsorption of carbon dioxide and hydrogen in dealuminated zeolites and novel MOF materials”
Enrique Lima : UNAM → UL : 6 months (Annex 9)
Title: “Investigation of the diffusion in nanoporous materials using PFG NMR”
5 AT positions have been successfully achieved which correspond to a total of 48 months. Their scientific reports and the evaluation forms are included in annexes.
2 additional students from UNAM (Enrique Lima 6 months to UL and Angel Rivera Ortega 12 months to UP-UM2) and 1 other from UH (Yunier Garcia Basabe 6 months to UP-UM2) are starting
their stays in EU host laboratories. Their CVs and all the filled NANOGASTOR procedures are provided in Annexes.
The NANOGASTOR is then offering a complete training for 8AT for a total duration of 72 months.
The slight deviation with the initial plan (9 AT for a total duration of 66 months for the 2 first years) comes from the fact that both Sandra Loera and Angel Rivera Ortega agreed with the host institution UP-UM2 that they would need 12 months instead of 6 months to be familiar with the complex Microcalorimetry and modelling techniques and then to be able to collect some meaningful results on the wide range of systems they plan to investigate. .
1.1.2 Initial Objectives From LA to LA
1stYear 2ndYear
Nothing 1 AT (6 months)
Global: 6 months
The AT position planned for the 2nd Year has been fulfilled by Leslie Reguera Núñez, PhD student from UH to UNAM (Annex 6).
1.1.3. Perspectives for the 3rdYear
The total number of AT man months initially planned is 108 months. 78 months have been already allocated which means that 30 months are still available. During the 2ndYear meeting in Rio, it was decided that 2 master students from UFRJ will visit UP and CSIC for 6 months each and 3 PhD students from UH will visit UCL, UP and UL for 6 months as well. These exchanges are planned to start before March 2009 to be achieved before November 2009 when the project, if extended, will be finished.
1.2 Research training
1.2.1 Initial Objectives from EU to LA & EU to LA
During the second Year, only 1 RT position has been used by R. Ruiz Salvador to visit Montpellier.
Initially, 10 RT positions have been planned which means that 7 RT positions are still available. It was decided the following schedule during the second Year meeting in Rio :
N. Rosenbach from UFRJ to UM2
G. Fetter, supervisor of A.Rivera Ortega from UNAM to UM2 H. Pfeiffer from UNAM to UM2
R Ruiz Salvador from UH to UCL M. Camblor from CSIC to UNAM G. Maurin from UM2 to UH.
This choice has been done to favour interactions between the supervisors of the home and the host institutions visited by the exchanged students during the last Year of the project.
2. Meetings
Initial Objectives and slight deviation from the original plan
2ndYear Meeting in Rio
This meeting was held in Rio de Janeiro during two days (2nd-3rdJune 2008) and has been organised by UFRJ (Annex 10). As initially budgeted, not all the institutions have been represented in this meeting.
Here is the list of the participants :
Heriberto Pfeiffer (UNAM) Claudio Mota (UFRJ) Celia Ronconi (UFRJ)
Jussara Miranda (UFRJ) Rabdel Ruiz Salvador (UH) Philip Llewellyn (UP) Guillaume Maurin (UM2) Alvaro Sampieri (UCL)
This meeting was also followed by 10 brasilian students interested to be sponsored by the NANOGASTOR project. During this project meeting, a training tutorial given by Dr. P. Llewellyn provides a great opportunity for these students to learn more about the synthesis of nanoporous materials as well as the experimental techniques used to characterize their adsorption properties. This training program has been completed by a brief overview from D. G. Maurin on the simulation techniques used to deeper understand the microscopic mechanisms involved in the adsorption process.
This meeting offered us the opportunity to plan everything for the last Year of the project in terms of student (AT) and experienced (RT) researchers.
4. Scientific production
As mentioned in the introduction, the research effort performed by the exchanged students on the structure prediction and the adsorption properties of novel nanoporous materials including zeolites and Metal Organic Frameworks, was awarded by a list of papers published in the best journals of Chemistry including J. Phys. Chem. B, J. Am. Chem. Soc., Angew. Chem. where the ALFA-II NANOGASTOR project was acknowledged. Some of the papers include the names of two exchanged students which highlight the strong interactions within the project. These papers are provided in Annex.
4.1 Most significant publications in international Journals
Predicting the flexibility of MOF systems from thermodynamic criteria : combination of microcalorimetry and molecular simulations to follow the adsorption behaviour of C1-C4 hydrocarbons and carbon dioxide in MIL-53-Cr, P.L. Llewellyn, G. Maurin, S. Loera-Serna, N.
Rosenbach, T. Devic, C. Serre, S. Bourrelly, P. Horcajada, Y. Filinchuk & G. Férey, J. Am. Chem.
Soc., 130, 38, 12808, 2008.
Combined Quasi-Elastic Neutron Scattering and Molecular Dynamics study of methane diffusion in Metal Organic Frameworks MIL-47(V) and MIL-53(Cr), N. Rosenbach, H. Jobic, A. Ghoufi, F.
Salles, G. Maurin, S. Bourrelly, P.L. Llewellyn, T. Devic, C. Serre & G. Férey. Angew. Chem. Int.
Ed.,47, 6611, 2008
Following the complex flexibility of MIL53Fe with gaseous hydrocarbons via in situ adsorption/
XRPD. Llewellyn, P. L.; Maurin, G.; Devic, T. ; Loera-Serna, S.; Rosenbach, N.; Serre, C.; Bourrelly, S.; Horcajada, P.; Filinchuk, Y. and Férey, G. Chem. Mater, 2008, in press.
¨Hydrogen Storage in Porous Cyanometalates: Role of the Exchangeable Alkali Metal¨. L. Reguera, J. Balmaseda, L. F. del Castillo, E. Reguera, J. Phys. Chem. C 2008, 112, 5581.
“H2storage in Copper Prussian blue analogues. Evidence on H2 coordination to the copper atom”, L. Reguera, C. P. Krap, J. Balmaseda, E. Reguera; J. Phys. Chem. C, 2008, 112, 15893.
¨Hydrogen Storage in Porous Transition Metals Nitroprussides¨. L. Reguera, J. Balmaseda, C. P.
Krap, E. Reguera, J. Phys. Chem. C 2008, 112, 10490.
“Porous framework of T2Fe (T = Co, Ni, Cu, Zn) and H2 storage”, M. Avila, L. Reguera, J.
Rodriguez-Hernandez, and E. Reguera. Journal of Solid State Chemistry, in press.
“H2 storage in zeolita-like cyanometalates. Role of the building block”, L. Reguera, M. Avila, J.
Balmaseda, E. Reguera, J. Phys. Chem., C, in press
H2adsorption in porous solids with open metal sites, C. P. Krap, L. Reguera, J. Balmaseda, L. F. del Castillo, E. Reguera. in press.
2 Participation in Conferences
1st International Conference on Metal-Organic Frameworks and Open Framework Compounds, Augsburgh (Germany) 8-10 October 2008.
2ndEuchems Chemistry Congress, Turin (Italy) 16-20 September 2008.
COPS VIII 8th International Symposium on the Characterisation of Porous Solids, Edinburgh (Scotland), 10-13 June 2008.
31stBritish Zeolite Conference, Kiele (England), 2-4 April 2008 Nanoporous materials V, Vancouver (Canada), 25-28 May 2008.
4thInternational FEZA Conference, Paris (France) 2-6 September 2008.
5. Website :http://www.ucl.ac.uk/~uccaw3n/
This website was built in close collaboration between UP and UCL and it is hosted by UCL university as previously metionned. The information available online will be updated soon after the problems previously mentionned. The objective of this website is to allow a large diffusion of the project (open positions for the students, publications, thematic area) and to enhance the communication between the partners. In addition several partners advertise the NANOGASTOR project as you can see in the following personal websites :
http://www.lpmc.univ-montp2.fr/~gmaurin/fegh6.htmfrom the co-ordinator http://imre.oc.uh.cu/webzeolitas/news.phpfrom Rabdel Ruiz Salvador (Cuba).
ANNEX 1
Document for Alvaro Sampieri
Annex 1
Alvaro Sampieri
Home university: UNAM, Mexico Host university: UCL, London, UK
From August 20th2007 to August 20th2008 Alvaro Sampieri documents
Scientific report
NANOGASTOR student evaluation form
Scientific report : “Computational design of new hypothetical zeotype MOFs”
Supervisor : Dr. C. Mellot-Draznieks, Dr. D. Lewis, UCL, London.
Activities
Over the past twelve months, we have carried out computational studies of a series of hypothetical MOFs based on zeotype framework. In doing so our aim is first to establish a methodology applicable for such materials, secondly to explore the potential of these materials in advanced applications such as gas storage. This report summarizes the work and training undertaken. In outline:
Contextualization of the project through one course of modelling simulation concepts and articles.
Design of hypothetical zeotype metal organic frameworks.
Geometry optimization of hypothetical zeotype-MOFs.
Papers for submission
Introduction
Metal organic frameworks (MOFs) are hybrid materials built from metal ions with well-defined coordination geometry and organic bridging ligands [1]. The structures of MOFs are mainly based on a variety of topologies having 1D, 2D, and 3D pores [2]. In zeolites, for example, the pores are generally in a narrow range of sizes, 2–14 Å, while in MOFs this range is wider, 2–30 Å, [3]. The variety of frameworks in MOFs, with a pore size range, enables such materials to provide a diverse
‘space’ within which organic groups may be positioned to tailor specific properties of inorganic–
organic solid hosts [4] [5]. The conceptual approach by which a metal–organic framework is designed and assembled, in terms of reticular synthesis, is based upon identification of how building blocks come together to form a net [3].
Whereas the rational synthesis of hybrid frameworks is an extremely active and rapidly expanding field, the structure prediction of hybrid frameworks using computational chemistry is only at its early
stages. In such a context, simulations may be highly valuable to anticipate the crystal structures of isoreticular structures, especially in the absence of single crystals, and to help the structure elucidation from powder data [6]. For instance, with the Automated Assembly of Secondary Building Units (AASBU) method, Mellot-Draznieks et al. [7] [8] have shown that the incorporation of pre-defined building-unit in simulations is highly valuable, allowing to produce new inorganic open-frameworks containing targeted local structures of interest (double-four ring or sodalite cages, for example).
Furthermore, the synthesis metal-organic frameworks through preparation of polyoxometallates (POMs) or ε-Keggins into hybrid organic–inorganic materials have also studied [9]. Indeed, the POMs are versatile inorganic building blocks, which offer four anchorage points to an O-bridging ligand through its four capping metal ions.
In this context, we report the mainly results concerning the study of computational designing of new hypothetical metal-organic frameworks showing zeolite topologies. Geometry optimizations of hypothetical MOFs are also presented.
Building hypothetical zeotype metal-organic frameworks
Hypothetical zeotype MOFs were computationally built using a polyoxometallate (POM) bridging to an organic ligand. The POM ion, Figure 1A, was composed by Mo12La4O36and no solvent (i.e. water) or nor terminal H (like OH) were considered in order to reduce computational cost. The organic ligand was the terephthalic acid or benzene-1,4-dicarboxylic acid (BDC), Figure 1B.
Figure 1. Mo12La4O36polyoxometallate (A) and terephthalic acid (B).
Using POMs and BDC ligands described above a number of hypothetical MOFs based on known zeolite frameworks (www.iza-structure.org/databases/) were constructed and geometrically optimized
(A)
Mo (B)
La O
using empirical force filed [10-13] by using Cerius2package. A typical hypothetical MOF structure with the ABW topology is represented in Figure 2.
Figure 2. Hypothetical ABW topology built through O-bridging of a POM and BDC.
Results
Universal force field (UFF) and charges equilibration (QEq) methods [14] were used to carry out the energy minimizations of different hypothetical zeotype MOFs. Framework energy values of known zeolite, previously reported by Foster et al. [15], were plotted against the framework density (FD = Si tetrahedrons in 1000 A3) in order to compare with our results, Figure 3. In the hypothetical topologies the FD was estimated by the number of POM occupying in a volume of 10-4 A3 in a cell unit. The total framework energy (Kcal/mol) was divided by the number of Si in zeolite or POM in hypothetical topologies and referred to the framework energy of quartz.
12 14 16 18 20 22 24 26 28 0
1 2 3 4 5 6
DDR
TotalEnergy(x10-3 Kcal/mol)
FD (TdSi) CAN
HEU MEP
SOD MOR DFT
AFN AHT ACO
ATV AFO VET
TON BIK AEN AFI
LTL THO LTA FAU
GIS ANA MER
MTW
quartz
4 5 6 7 8 9 10
0 2 4 6 8 10 12 14
DDR
FrameworkEnergy(Kcal/mol)
FD (POM*100000 amg/Cell Vol) CAN
HEU
MEP SOD
DFT AFN AHT ACO
AFO THO
quartz MOR
ATV VET
TON BIK
AEN AFI LTL
LTA
FAU
ANA GIS
MER MTW
Figure 3. Framework energy comparison of Zeolite (A) and hypothetical zeotype MOFs (B). In both cases the energies are normalised to the result obtained for the quartz topology.
It is well-known that framework energy in zeolites has more or less a linear trend with framework density (Figure 4). In fact, if the zeolites became denser (high values of FD), then, they are more crystallinity and structurally stables. For instance, BIK, TON, ATV and MTW are zeolites with an excellent stability, in contrast to THO, FAU, LTA and ACO. Surprisingly, the hypothetical MOFs topologies seem to have an opposite behaviour, which could be due to topological geometry differences between zeolites and hypothetical zeotype structures. The bonds among oxygen and silicon atoms in zeolites are very strong and could also become flexible. However, in the hypothetical structures, the oxygen atoms in BDC are bonded to lanthanum (in POMs) and this bond cannot be as flexible as in the Si tetrahedron of zeolites, because BDC is a rigid molecule. Although, the new hypothetical MOFs do not necessary show the same stability as zeolites, they showing a wide range of cavities and pores to open new possibilities in the synthesized of new MOFs.
Conclusion
Building of new hypothetical MOFs were successfully built with zeolite topologies. We shall continue to investigate the perhaps surprising result that the framework stability does not correlate with density; moreover, this result may direct further experimental work. This preliminary study opens new perspectives in the preparation of new hybrids.
References
1. Figueroa, J. D.; Fout, T.; Plasynski, S.; McIlvried, H.; Srivastava, R. D., Int. J. Greenhouse Gas Control 2008, 2, 9-20.
2. Stuart R. Batten, R. R., Angew. Chem. Int. Ed. 1998, 37, 1460-1494.
3. Ockwig, N. W.; Delgado-Friedrichs, O.; O'Keeffe, M.; Yaghi, O. M., Acc. Chem. Res. 2005, 38, 176-182.
4. Papaefstathiou, G. S.; MacGillivray, L. R., Coord. Chem. Rev. 2003, 246, 169-184.
5. Suh, M. P.; Cheon, Y. E.; Lee, E. Y., Coord. Chem. Rev. 2008, 252, 1007-1026.
6. Mellot-Draznieks, C., J. Mater. Chem. 2007, 17, 4348-4358.
7. Caroline Mellot Draznieks, J. M. N. A. M. G. C. M. F. G. F., Angew. Chem. Int. Ed. 2000, 39, 2270-2275.
8. Mellot-Draznieks, C.; Girard, S.; Ferey, G., J. Amer. Chem. Soc. 2002, 124, 15326-15335.
9. Dolbecq, A.; Mellot-Draznieks, C.; Mialane, P.; Marrot, R.; Ferey, G.; Secheresse, F., Eur. J. Inorg. Chem. 2005, 3009-3018.
10. Rappe, A. K.; Colwell, K. S.; Casewit, C. J., Inorg. Chem. 1993, 32, 3438-3450.
11. Casewit, C. J.; Colwell, K. S.; Rappe, A. K., J. Amer. Chem. Soc. 1992, 114, 10035-10046.
12. Casewit, C. J.; Colwell, K. S.; Rappe, A. K., J. Amer. Chem. Soc. 1992, 114, 10046-10053.
13. Rappe, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A.; Skiff, W. M., J. Amer. Chem. Soc. 1992, 114, 10024-10035.
14. Rappe, A. K.; Goddard, W. A., J. Phys. Chem. 1991, 95, 3358-3363.
15. Foster, M. D.; Simperler, A.; Bell, R. G.; Friedrichs, O. D.; Paz, F. A. A.; Klinowski, J., Nat. Mater. 2004, 3, 234-238.
STUDENT OR SCHOLAR EXCHANGE EVALUATION FORM Name (as appears on the passport) Alvaro Sampieri
Mobility title Computational design of new hypothetical zeotype MOFs
Home institution UNAM, Mexico
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ANNEX 2
Document for Sandra Loera
Annex 2
Sandra Loera
Home university: UNAM, Mexico city, Mexico Host university: UP, Marseille, France
From October 1st2007 to October 1st2008 Sandra Loera documents
Scientific report
NANOGASTOR publications
NANOGASTOR student evaluation form
Scientific report : Experimental investigation of the adsorption of alkanes in MOF systems- Synthesis of novel materials
Supervisor : Dr. P.L. Llewellyn, Laboratoire Chimie Provence,Université de Provence.
A. Adsorption hydrocarbons in MIL47 (V) and MIL53 (Cr, Fe & Ga) 1. Introduction
MOFs (Metal Organic Frameworks) have been extensively used in the gas storage specially of hydrogen1-3 and carbon dioxide4-8. The pore diameter of some MOF are closed to the critical dimensions of many important hydrocarbons molecules, which make the transport processes in these nanoporous system considerably more complex than adsorption in homogeneous phases and in macroporous systems.
Adsorption behavior of hydrocarbons in zeolites have been frequently reported in the literature, moreover, no experimental data exist on adsorption hydrocarbons of MOF materials.
In this study, the adsorption isotherms, the X-Ray diffraction spectra of C1-C4 hydrocarbons, including propylene and propyne in MIL47 (V), MIL53 (Cr) and MIL53 (Fe) have been systematically investigated using a gravimetric method, microcalorimetry method and in-situ synchrotron powder diffraction experiments.
2. Results and discussion
Several techniques were used in the study of hydrocarbons adsorption in MOF, the results of these studies are presented below. The comparison between different metal organic-framework structures permitted to obtained information about the mechanism of hydrocarbon adsorption on flexible and non- flexible materials. Furthermore, the calorimetric measurement obtained during the adsorption give information on the energetic nature of adsorbents which can be of importance to characterize solids in terms of specific adsorption sites and defects.
2.1. Adsorption gravimetry. The adsorption isotherms for MIL53 (Cr) and MIL53 (Fe) obtained at 303K are given in figures 1-2, respectively. The results are presented in standard form and in semi-log form in order to highlight the low pressure steps.
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
0 5 10 15 20 25 30
p / bar va/cm3liqg-1
CH4
C2H6
C3H8
C4H10
0 1 2 3 4 5 6
0.1 1 10 100
p / bar Na/molec.u.c.-1
CH4
C2H6
C3H8
C4H10
Figure 1. Isotherms ((a) standard and (b) semi-log scale) obtained at 303K during the adsorption of the C1 – C4 hydrocarbons on MIL-53 (Cr).
(a) (b)
The isotherms given in figure 1(a), are of Langmuir type when reported in a standard form as amount adsorbed (as cm3liq g-1) versus pressure. However, when plotted as the number of molecules adsorbed per unit cell as a function of the log of the pressure (figure 1(b)), one can distinguish a step in the C3 and C4 isotherms whilst a convex shape is obtained for the C2 adsorption. By contrast, only a concave profile is pointed out for C1 which is commonly observed when plotting a Langmuir isotherm for a rigid microporous material. The steps in the C3 and C4 isotherms may be the signature of the breathing of the MIL53 (Cr) structure upon adsorption as was previously observed for carbon dioxide.4,8 Further, the convex profile observed for C2 may be assigned to an intermediate behavior between the two types of isotherms. Furthermore, whilst the amounts adsorbed in terms of liquid volume increase from methane to propane, the opposite trend is observed in terms of number of molecules per unit cell. It is of interest to use both scales as this shows the paradox between macroscopic (liquid volume) and microscopic (number of molecules per unit cell) representations of the adsorption data. Indeed, both representations are of interest with respect either to applications or when comparing to molecular modeling for example.
0 1 2 3 4 5 6 7
0 5 10 15 20 25
p / bar na/mmol.g-1
CH4 C2H6
C3H8
C3H6
C4H10
0 1 2 3 4 5 6 7
0.1 1 10 100
p / bar na/mmol.g-1
CH4 C2H6
C3H8 C3H6
C4H10
Figure 2. Isotherms ((a) standard and (b) semi-log scale) obtained at 303K during the adsorption of the C1 – C4 hydrocarbons and C3H6on MIL53 (Fe).
For all the hydrocarbon molecules, several steps in the isotherms are visible for MIL53(Fe) (figure 2).
Methane shows negligible uptake to a pressure of 10 bars before a small step to an uptake of around 1.4 mmol·g-1. The other hydrocarbons studied here also show a step corresponding to the same amount of adsorbed species, but also a second one, related to an uptake of around 2.8 mmol·g-1. A third step is also observable although not always complete in these isotherms. For C2H6and C3H6, this last step correspond to the adsorption of around 6.8 mmol·g-1.
2.2. In-situ X ray powder diffraction. X-Ray Powder Diffraction (XRPD) patterns were collected during the hydrocarbon adsorption using a specific adsorption apparatus developed for experiments at the Swiss-Norvegian beamline at the ESRF for MIL53 (Cr) and MIL53 (Fe).
All the X-ray diffraction patterns (figure 3) show that the initial adsorption of gas occurs in the outgassed, large pore form of MIL53 (Cr). In the case of methane, this large pore version is observed throughout the adsorption whatever the pressure, even up to 60 bars. A different behavior is observed in the case of the C2 – C4 hydrocarbons. The initial large pore form is visible at low pressures before the observation of a coexistence of phases between the large and narrow pore forms. Indeed, the pure narrow pore phase exists only in a very small range of pressure (≈ 0.3 bar for ethane, 0.16 bar propyne, 0.2 bar propylene, 0.1-0.2 bar for propane and 0.1 bar for butane). At higher pressures, the system again is biphasic up to 1.8 bars for ethane, 0.51 bars for propyne, 0.5 bars for propylene, 1.5 bars for propane and 0.5 bar for butane where the expanded phase appears alone. At higher pressures the large pore form is again observed. This large narrow large pore transition with gas filling has been termed ‘breathing’ in the case of carbon dioxide.8 The difference observed here in the case of the hydrocarbons is that the narrow pore form is present in only a small region of pressure.
(a)
(b)
XRPD shows unambiguously the evolution of the flexible character of the MIL53 (Cr) structure with the hydrocarbon chain length. Once identified the peaks corresponding to the large and narrow forms, cell parameter refinements were performed (tables 1 and 2). The unit cell volume of the narrow pore version increases from 1258.7(1), 1275.6(1) to 1370.8(1) Å3for ethane, propane and butane,
respectively in relation with steric effects. This steric feature of the hydrocarbons significantly limits the degree of contraction when compared with smaller sorbates such as carbon dioxide (V = 1072 Å3
7) and water (V = 1012 Å3 9), respectively. The reopening of the structure at higher pressure
unambiguously shows the presence of the only large pore version (figure 3) and volumes only slighter higher than those observed for the outgassed structure (table 1).
The XRPD patterns of MIL53 (Fe) (figure 4) show clear changes in the crystalline structure, as a consequence of the gas adsorption into the channels.
Except for the methane adsorption, where only two different patterns are observed for the adsorption up to 50 bars, all the studied hydrocarbons (C2H6, C3H4, C3H6, C3H8, C4H10), shows four different XR patterns according to the gas pressures Moreover, the pressures associated with the changes in the XR diagrams are in perfect agreement with the ones of the steps in the adsorption isotherms. One can thus anticipate that the steps are associated with structural modifications. A first analysis of this structural data can be obtained by relating the cell volume of the MIL-53 (Fe) phase (for a given form) and the volume of the adsorbed probe molecule (Table 3-5). It can be seen for the saturated hydrocarbons that the volume of both intermediate phases slightly increases with increasing volume of the probe molecule.
2.3. Adsorption microcalorimetry. The adsorption isotherms obtained at 303 K for MIL47 (V) are given in figure 5. Simple, type–I isotherms can be observed for all the hydrocarbons. Relatively constant enthalpies were obtained for C2H6, C3H4, C3H6and C3H8, suggesting that the interaction of adsorbate molecules with an energetically homogeneous surface. Peaks in the calorimetric curve occur where phase transition occur in the adsorbed phase.9-10 Neutron diffraction studies will be necessary for determine if the enthalpy peak for butane adsorption on MIL47 (V) is due to a phase change.
The adsorption isotherms obtained by gravimetry have a good agreement with gravimetry isotherms for MIL53 (Cr & Fe) (figures 6(a) and 7 (a)). But is important to analyze the increase or decrease of the enthalpies in the steps for each isotherm. In the low domain of pressure for C2 to C4 hydrocarbons, the enthalpies increase up to a maximum, and then slightly decrease with the pressure for MIL53 (Cr) (Figure 6 (b)).
Figure 3. Variation of the XRPD patterns of MIL53 (Cr) with the alkane pressure at 303 K (~0.71110 Å). Black: large pore form (empty pores); red: mixture of narrow and large pore form; blue: large pore form (pores filled). Main peaks
belonging to the narrow pore form are highlighted/circled.
Gas a(Å) b(Å) c(Å) β(°) V(Å3) Pressure (bar)
CH4 --- --- --- --- --- --- C2H6 19.24(1) 9.89(1) 6.94(1) 107.52(1) 1258.7(1) 0.75 C3H4 19.674(3) 8.988(2) 6.803(1) 107.39(2) 1148.0(4) 0.04 C3H6 19.697(2) 9.277(1) 6.834(1) 107.83(1) 1188.8(3) 0.038 C3H8 19.24(1) 10.08(1) 6.96(1) 109.12(1) 1275.6(1) 0.1 C4H10 20.30(1) 10.60(1) 6.90(1) 112.55°(1) 1370.8(1) 0.1
Table 1. Cell parameters of the narrow pore forms for MIL53 (Cr) in presence of C3H4, C3H6and C1-C4 hydrocarbons (space group C2/c).
Gas a(Å) b(Å) c(Å) V(Å3) Pressure (bar)
- 16.733(1) 13.038(1) 6.812(1) 1486.1(1) 0
CH4 16.444(1) 13.512(1) 6.834(1) 1518.6(1) 33 C2H6 16.109(1) 13.938(1) 6.836(1) 1535.0(1) 13.5 C3H4 15.9381(8) 14.1412(7) 6.8425(3) 1542.2(1) 4.8 C3H6 16.1040(8) 13.9625(8) 6.8407(3) 1538.2(1) 10.2 C3H8 16.190(1) 13.820(1) 6.835(1) 1529.4(1) 10 C4H10 16.103(1) 13.925(1) 6.833(1) 1532.4(1) 0.5
Table 2. Cell parameters of the large pore forms for MIL53 (Cr) in presence of C3H4, C3H6and C1-C4 hydrocarbons (space group Imcm).
This behavior was previously observed for carbon dioxide.4,8 Here, the initial enthalpy values observed for all hydrocarbons are due to the adsorption in the large pore outgassed form of MIL53(Cr). Further, the maximum value in the enthalpies corresponds to a pressure at which the narrow pore structure starts to appear. This observation is not so surprising as an increase in molecular confinement results in an enhanced interaction of the probe molecule with the pore wall.