Bio-based porous materials for hydrogen storage and environmental applications

Estimated results

The results on the preparation and investigation of the new bio-based derived materials, performance on hydrogen storage and environmental remediation will be valorized in at least 5 manuscripts published in high-impact ISI ranked journals; 1 patent request (OSIM), detailed scientific reports.

Objective 1: Design, obtaining and morpho-structural investigation of CNMSs resulted through biomass thermo-chemical conversion, including surface chemical functionalization and porosity enhancement. 2 manuscripts submitted for evaluation to high-ranked ISI journals.

Objective 2: Design and preparation of porous polymeric composites of p-HEMA with embedded carbon nano / microstructures (CNMSs). 2 works presented at international conferences; 1 manuscript submitted for evaluation to a high-ranked ISI journal; 1 national patent request.

Objective 3: Testing and morpho-structural adaptation of engineered porous polymer composites for hydrogen storage and environmental remediation. 2 works presented at prestigious international conferences; 2 manuscripts submitted for evaluation to high-ranked ISI journals; 1 extensive research report.

Phase I

Phase 1 of the BIOPOROMAT project consisted in 5 research activities. All of them were realized in time, which led to the achievement of the 2022 project objectives and overcoming the project results deliverables. A brief description of these activities is presented in the following paragraphs.
Act. A1.1 refers to the evaluation of the availability and types of biomass wastes and to chemical, morphological and structural characterization of some lignocellulosic biomass in order to have a realistic assessment on the valorization potential as well as on the pre-treatments of the feedstocks subjected to thermochemical conversion processes.
Considering the findings generated in this stage, the activity had as result the design of biomass wastes processing flow (feedstock, pre-treatments, conversion path) that will be integrated in a multi-stage protocol in order to obtain an innovative material with tailored properties which feature an organic core (CMNS) and a polymeric outer layer.
Act 1.2 presents 2 synthesis methods to prepare carbonaceous materials micro and nano structured through slow pyrolysis and hydrothermal conversion.
The experimental devices and facilities were adapted and work protocols were developed. Two laboratory-scale reactors, equipped with a heating system and temperature and pressure control were used in order to obtain CMNSs. In the same context, preliminary tests were carried out in an experimental configuration that allows thermal processing using a system equipped with a CO2 laser and a displacement in x, y coordinates (Act 1.3).
As a result of experimental (Act 1.4), relevant data were obtained regarding the chemical, morphology and structural characterization of CNMS obtained in previous activities. Several advanced characterization methods including FT-IR spectroscopy, SEM scanning electron microscopy, Raman spectroscopy, TGA thermogravimetric analysis and dimensional analysis were used. Along with the preliminary evaluation of porosity characteristics (Act 1.5) as well as the estimation of the CNMS functionalization possibilities, all data generated in the first phase allow the design of porous materials with tailored properties adapted to the targeted applications in this project (environmental remediation and hydrogen storage).

Results indicators

Articles submitted/accepted for publication in ISI Q1 ranked journals:

1. Ungureanu G., Bejenari I., Hristea G., Volf I., 2022, Carbonaceous materials from forest wastes conversion and their corresponding hazardous pollutants remediation performance, Forests, 13(12), 2080; https://doi.org/10.3390/f13122080 Q1, IF3.282.
2. Stan L., Volf I., Stan C.S., Albu C., Coroaba A., Ursu L.E., Popa M., Intense blue photo emissive Carbon Dots prepared through pyrolytic processing of lignocellulosic waste, Nanomaterials Q1, IF 5.719, 2023, 13, 131, DOI: 10.3390/nano13010131.

Articles published in international data bases journals (BDI):

1. Armanu G.E., Volf I., 2022, Natural carriers for bacterial immobilization used inbioremediation, Bulletin of Polytechnic Institute of Iasi, Chemistry and Chemical Engineering section, 68 (72), 3, 109-122. http://www.bipcic.icpm.tuiasi.ro/2022_68_3.html

Communications:

1. Armanu G. E., Tofanica B.M., Volf I., 2022, Measurement of key compositional parameters in three type of biomass wastes in order to define the appropriate feedstock for thermochemical conversion, The 6th International Conference on Chemical Engineering ICCE2022, Advanced Materials and Processes for a Sustainable Development, http://www.cercetare.icpm.tuiasi.ro/conferinte/ICCE2022/pdf/ICCE2022-program.pdf
2. Armanu G. E.,Tofanica B.M., Secula M. S., Mamaliga I.,Volf I.,2022, Predictive carbonaceous materials yields resulted from carbonisation in relation with the main components of the feedstock, SICHEM 2022, Hydrogen the future energy and chemical engineering vector,

 https://sicr.ro/wp-content/uploads/2022/11/SICHEM_Program_2022_v12.pdf

3. Asoltanei A.M., Iacob Tudose E., Secula M.S.S., Mamaliga I., 2022, Effective diffusivity in porous spherical and cylindrical particles, SICHEM 2022, Hydrogen the future energy and chemical engineering vector.

https://sicr.ro/wp-content/uploads/2022/11/SICHEM_Program_2022_v12.pdf

Workshop (11.07.2022).

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Phase II

Phase 2 (2023) of the project Porous materials derived from biomass waste with environmental applications and hydrogen storage (BIOPOROMAT) consisted in nine scientific research activities. The activities within this stage were carried out in full and within the assumed deadline, which led to the fulfillment of the objectives for the year 2023. The specific scientific indicators of phase 2 have also been accomplished. A synthetic description of the main activities carried out in this phase is presented herein further.

Act. 2.1. focused on the porosity adaptation of the obtained CMNS. Based on experimental data achieved, the activity resulted in the validation of three distinct working protocols for the adaptation of the porosity/functionalization of the CMNS in direct correlation with the applications targeted in this project.

Act 2.2. and Act 2.3. (continuation of activities Act 1.2. and Act 1.3.) concludes some aspects that bring conceptual and methodological insights on the approached thermal conversion processes (pyrolysis, hydrothermal carbonization). The results obtained during the activities of Act. 2.4. and Act. 2.5. pointed out the influence of the activation/functionalization treatments on the structures and properties of the studied materials.

In Act 2.6. the research was focused on the design and achievement of two types of polymer gels that act as matrices for the CMNS embedment in order to obtain a material with high added value and a wide range of applications: (i) designing and obtaining a polymer-based hydrogel natural (gellan); (ii) designing and obtaining a cryogel based on Poly(2-hydroxyethyl methacrylate) (p-HEMA). The carbon structures (functionalized or not) obtained in the previous activities were successfully incorporated into both polymer matrices (Act 2.7.).

In Act 2.8. relevant information was obtained regarding the structure/properties of previously obtained polymer composites using advanced characterization methods including: FT-IR spectroscopy, scanning electron microscopy, SEM, but also their specific behavior in systems: determination of stability, degree of swelling, etc.

Following the critical evaluation of the large volume of experimental data obtained at this stage and considering the targeted applications as well as the preliminary tests performed, in Act 2.9. the configurations of the composite materials that will be considered in the testing phase were validated.

All the data obtained in phase II allow obtaining complex composite materials with properties adapted to the applications targeted in this project (remediation of environmental factors and storage of alternative forms of energy).

Results indicators

Articles submitted/accepted for publication in ISI Q1 ranked journals:

1. Hristea G., Iordoc M., Lungulescu E.M., Bejenari I. and Volf I.*, 2023, A sustainable bio-based char as emerging electrode material for energy storage applications, Scientific Reports, (Q1), (FI 4.6), under evaluation, submission ID 8684c3ca-aab7-4561-8de5-b7fc11218059.
2. Mikhailidi A., Ungureanu E., Belosinschi D., Tofanica B.M.* and Volf I.* , 2023, Cellulose-Based Metallogels – Part 3: Multifunctional Materials, Gels, 9(11), 878. (Q1) (FI 4.432), https://doi.org/10.3390/gels9110878.
3. Ciuperca O.T., Ionescu E., Secula M.S., Volf I.*, 2023, Microwave-Assisted Extraction of Condensed Tannins from Branches of Prunus spinosa L.: Response Surface Modeling and Optimization, Processes, 11, 2024, https://doi.org/10.3390/pr11072024 (Q2), (FI 3.5).
4. Tincu C., Hamcerencu, M., Secula M.S., Stan C.S., Albu C., Volf I., Popa M., Gellan-based Hydrogel Particles Cross-linked with Fe³⁺ Ions and Loaded with Carbonaceous Nano/Microstructures designed for environmental remediation, International Journal of Molecular Sciences, (Q1), (FI 5.6), under evaluation, submission ID ijms-2771027.

Patent request:

1. Stan C.S., Albu C., Volf I. Procedure of valorization of some lignocellulosic wastes in a porous polymer composite for wastewater treatment, A/00677 / 10.11.2023.

Articles published in international data bases journals (BDI):

1. Toma A.C., Volf I., 2023, A short review on urban air pollution and innovative bio-remedial approaches, Bulletin of Polytechnic Institute of Iasi, Chemistry and Chemical Engineering section, 69 (73), 3, 87-101, doi.105281/zenodo.10072450.

Communications:

1. Armanu G.E., Secula M.S., Volf I., 2023, Eco-efficient hydrochar for immobilization of Pseudomonas species, The 12th International Conference on Environmental Engineering and Management ICEEM 12, Circular Economy and Sustainability, https://www.iceem.tuiasi.ro/wp-content/uploads/ICEEM12_Program-04.09.2023_f.pdf
   
2. Armanu G.E., Bertoldi S., Chauhan Z., Eberlein C., Nikolausz M., Shmidt M., Heipieper H.J., Volf I., 2023, Biodegradation of phthalic acid esters using immobilized bacteria on a natural carbonaceous porous material, Annual International Conference of the Association for General and Applied Microbiology, VAAM 2023, Göttingen, https://vaam.de/aktivitaeten/jahrestagung/archiv-der-jahrestagungen/

Workshop (14.07.2022).

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