Unraveling the Photobehavior of Novel Mixed-metal MOFs for Efficient New Photocatalysts

Project Information

MMOF4PPS

Grant agreement ID: 101032472

DOI

10.3030/101032472

Project closed

EC signature date 28 April 2021

Start date 8 July 2021

End date 7 July 2023

Funded under

• EXCELLENT SCIENCE - Marie Skłodowska-Curie Actions

Total cost

€ 160 932,48

EU contribution

€ 160 932,48

Coordinated by

UNIVERSIDAD DE CASTILLA - LA MANCHA
Spain

Periodic Reporting for period 1 - MMOF4PPS (Unraveling the Photobehavior of Novel Mixed-metal MOFs for Efficient New Photocatalysts)

Reporting period: 2021-07-08 to 2023-07-07

Summary of the context and overall objectives of the project

The project was aimed at correlating the photocatalytic activity of bi and trimetallic mixed metal organic frameworks (MMOFs) with their photodynamic behaviour to boost research and development in this important field of photocatalysis by MMOFs. Catalysis is the only technical principle that saves both time and energy, thereby combining economic and ecological values. Approximately 95% of products and 80% of the added value in chemical industry are based on catalytic processes. In particular, European catalysis industry has a market value of several B€,1 thus representing a key technology for European economy, industry, growth and sustainable future. As demand is rising due to global population increase while climate and energy issues should be tackled, there is an urgent need to develop high performance (in terms of stability and robustness) and conceptually innovative catalysts. This is the challenge MMOF4PPS ambitions to tackle, through the design of novel materials improving the properties of homometallic Metal Organic Frameworks (MOFs) by the addition of another metal, bringing mixed-metal metal organic frameworks (MM-MOFs) exhibiting improved electronic conductivity and stability, and being potential alternatives to current catalysts for the production of high-value chemicals.
Importance to the society: Photocatalysis is deemed as an immensely useful alternative for avoiding the imminent energy crisis in the future. In recent times, mixed metal organic frameworks (MMOFs) have shown tremendous promise as heterogenous catalysts for environmentally and energetically important reactions. On the other hand, photodynamic properties of MMOFs have also been investigated for their fascinating optical properties. However, although there have been many scattered reports on the photocatalysis and photodynamics of MMOFs, reports trying to correlate the aforementioned properties of MMOFs. Hence, this current project serves a two-fold purpose. On one hand, efficient MMOF based photocatalysts were obtained that serve to solve the environmental and energetical issues. On the other hand, study of their photodynamic properties endow us the know-how of the causality associated to photodynamics and photocatalysis. Finally, these two aspects undertaken in this project shall open up new avenues for research and development in this field of research, thereby satisfying scientific and societal needs alike.
The main objectives and actions of MMOF4PPS will thus be to: (a) explore and optimize synthetic procedures for MM-MOFs, (b) decipher the ultrafast photo-processes inside MM-MOFs, (c) study the effect of varying ratio of different metal clusters on the photocatalytic performance, (d) gain detailed knowledge of the effectiveness of MMMOFs over single metal MOFs in photocatalysis and (e) develop structure–(photocatalytic) activity relationship.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

1) 1-9 months: Herein we performed an exhaustive and systematic spectroscopic and photodynamical characterization of three UiO-66-NH2-type MOFs, where the metal cluster composition is varied from 100% Zr, a mixture of Zr/Ce (80/20%), and a mixture of Zr/Ce/Ti (70/7/23%). This work has been published in the journal Materials Today: Energy.
2)9-18 months: In this work, a series of MMOFs with napthalene-2,6-dicarboxylate, were synthesized and characterized. The corresponding structural, chemical, photodynamics and photo response properties were investigated. This work is accepted in ACS Applied Materials and Interfaces.
3) 18-24 months : In this work, a series of mixed linker Zr based MOFs were synthesized and studied spectroscopically by varying the percentage of linkers, named NDC and DANDC. The manuscript has been communicated a few days ago.
4) 2 weeks in the 22nd month: Industrial training for the photocatlaytic degradation of toxic wastes in industrial wastewater and measurements of Biological Oxygen Demand, Chemical Oxygen Demand, Calcination and gravimetric experiments were performed.These tasks were performed in the presence of Dr. Anabela Nogueira, research engineer at Advantech Company.
Results: This was essentially an industrial training session combined, with no direct results to discuss. The objective of the secondment was to provide exposure to industrial techniques in the field of photocatalysis, as was mentioned in the grant agreement
5) Dissemination: Details of the so far dissemination activities are given as following:
a) November 16th, 2021: Science Week, Seminar titled ‘Oscillating Reactions’
b) November 9th, 2022: Group seminar, title: “Mixed metal MOFs as promising photocatalysts: an introductory talk”
c) 4th-7th June 2023: Scientific dissemination to students at Colegio Virgen del Carmen about spectroscopy, luminescent materials and its applications in optoelectronic devices and sensors. We also showed our laboratory and equipment.
d) The researcher has attended online seminars at the UCLM, Toledo University campus and of the department of physical chemistry. To mention a few, “Efecto de los Sustituyentes Voluminosos en la Relajación Fotofísica y Fotoquímica de un Derivado de Tetrafeniletileno. Implicaciones en el Mecanismo AIE (7th October 2022, online seminar)” “Chemistry of porous organophosphorus materials, from synthesis to future perspective, 19 may 2023” “Photo Physical Processes of Sulfur and Selenium Containing Model Molecules of Biological Significance (23rd June, 2022, online seminar)”, “
e) The researcher delivered two talks to the faculty of physical chemistry and biochemistry, UCLM on the 2nd and 16th of June 2023. The titles of the talks were as follows: (i) Correlating photocatalytic activity of mixed metal MOFs to their spectrodynamic behaviour; (ii) How much is too much? A guide to dope the correct % of Ce in naphthalene based MOFs for photocatalysis.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

From the article published in Materials Today: energy, our results have experimentally proved the direct relationship between the photodynamics of MMOFs and their improved photocatalytic activities. These results will undoubtedly serve as a guiding tool for a better designing of MMOFs where the LCCT reaction can be further promoted, and therefore, their photocatalytic activity further ameliorated. From the article in ACS Applied Materials and Interfaces, the results showed that the overall efficiency of the process is enhanced by 20% when the MOF is doped with 9% of Ce compared with the pristine Zr NDC MOF, providing clear findings to better design mixed Zr/Ce metal MOFs for sustainable photocatalytic applications. The third work, demonstrate the suppression of the well observed ET and Excimer formation in mixed napthalene linker based MOFs and predominance of LCCT phenomenon by simple introduction of amino group containing co-linker in the MOF clusters, which makes them ideally placed as potential candidates for photocatalytic applications in near future.

Graphical Abstract for Published Paper in Materials Today Energy

Graphiacl Abstract for article under review in ACS: Applied Materials and Interfaces