Bio-based porous materials for hydrogen storage and environmental applications

The project addresses an innovative and multidisciplinary idea that can open up further advances in the field of high-tech bio-based products, wastes conversion, porous materials, alternative energy storage, environmental remediation and sustainable design. This project aims to valorise a bio-based active rich carbon by-product, resulted as a solid phase from thermochemical conversion of biomass wastes, into an unprecedented polymeric cryogel with tailored porosity. The porosity and geometry of the new bio-based material can be controlled within broad limits of the experimental parameters specific to each stage and according with targeted applications. The research activities proposed in the project, also involve extensive testing and applications of the achieved composites in two high interest current trends: (i) in the fields of clean/renewable energy sources for hydrogen storage and (ii) in reducing the environmental impact (promising substrate in wastewater/gas streams purification). All the research will be conducted using the latest state of the art analytical tools, jointly agreed standard procedures and specific investigation and characterization tools (TGA, FT-IR, XPS, DLS, BET, SEM/TEM and AFM). The proposal goal is timely and in line with two important in progress EU initiatives: Bio Based Industries Joint Undertaking (bbi.europa.eu) and Hydrogen Europe (hydrogeneurope.eu).

Project concept

Summary of the activities carried out in the framework of this project:

The purpose of this project was to design and obtain hybrid materials based on carbon micro/nano structures (CMNS), resulting from the conversion of biomass waste, embedded in polymer matrices (natural or synthetic), with environmental and energy storage applications.

A summary of the main results obtained is presented beneath.

O1 focused on the evaluation and analysis of the availability and types of biomass waste, through the chemical, morphological and structural characterization of some lignocellulosic waste in order to achieve a realistic evaluation of the valorization potential as well as the establishment of their pretreatment and conversion techniques. The biomass wastes (spruce bark, vine wood and wheat straw, the necessary pretreatments (physical) as well as the thermochemical conversion techniques (slow pyrolysis at 550°C and hydrothermolysis at 260°C) were defined and their optimized protocols have been developed. CMNS have been extensively investigated.

O2 aimed at porosity tailoring for the obtained CMNS. Obtaining data through numerous experimental tests and evaluations, the activities resulted in the validation of three working protocols for the adaptation of the porosity/functionalization of the CMNS in direct correlation with the targeted applications. Two types of polymer gels were designed as matrices for embedding CMNS: (i) a hydrogel based on a natural polymer (gellan); (ii) a cryogel based on Poly(2-hydroxyethyl methacrylate) (p-HEMA) and one based on poly-acrylic alcohol (PAA) physically cross-linked with poly-vinyl alcohol (PVA), where carbon structures were embedded successfully; (iii) two configurations of hybrid materials based on CMNS functionalized for energy storage and bacterial immobilization (bioremediation) applications.

O3: The carried-out studies showed that the gels based on gellan and CMNS present an affinity for dyes (Crystal Violet and Methylene Blue) with better adsorption capacities at equilibrium than other gels reported in the literature. Also, removal rates of 70-97% were obtained for Pb(II) ions and emerging organic pollutants (diclofenac). One of the proposed configurations represents a remarkable protective support for bacterial immobilization that increases by 4 times the survival rate of Pseudomonas bacteria, and by 30% the bioremediation capacity of wastewater polluted with plasticizer agents (diethyl phthalate). In the alternative forms of energy storage, the supercapacitor characteristics of the hybrid carbon material were validated, as well as the ability to retain some gases (H2, N2, CO2) of the hybrid cryogels obtained within the project. Some of the proposed composite configurations could represent a good protective film for H2 storage containers, reducing the possibility of embrittlement of the metal ferrule.

Project Dissemination:

7 articles published in ISI journals (6 works in Q1, and 1 work in Q2 journals).
9 works communicated at international conferences.
1 paper submitted to an ISI Conference Proceeding.
3 patent requests registered to OSIM.
3 scientific reports.
1 webpage.

Result indicators:

1. Articles submitted to ISI journals (Q1)
   1. Tincu C., Hacerencu M., Secula M.S., Stan C.S., Albu C., Popa M., Volf I*., 2024, A natural Carbon Encapsulated In Gellan-Based Hydrogel Particles designed for Environmental Challenges, Gels,10, 713, https://doi.org/10.3390/gels10110713, (Q1, FI 5).
   2. Armanu G.E., Secula M.S., Tofanica B.M., Volf I*., 2024, The Impact of Biomass Composition Variability on the Char Features and Yields Resulted through Thermochemical Processes, Polymers, 16, 2334. https://doi.org/10.3390/polym16162334 (Q1 FI 4.7).
   3. Hristea G., Iordoc M., Lungulescu E.M., Bejenari I. and Volf I.*, 2024, A sustainable bio-based char as emerging electrode material for energy storage applications, Scientific Reports, 14(1), 1095. https://doi.org/10.1038/s41598-024-51350-x (Q1, FI 4.6).
   4. 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 5), https://doi.org/10.3390/gels9110878
   5. 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).
   6. Stan L., Volf I.*, Stan C.S.*, Albu C., Coroabă A., Ursu L.E., Popa M., 2023, Intense Blue Photo Emissive Carbon Dots Prepared through Pyrolytic Processing of Lignocellulosic Wastes, Nanomaterials, 13 (1), 131, https://doi.org/10.3390/nano13010131 (Q1, FI 5.719).
   7. Ungureanu G., Bejenari I., Hristea G., Volf I.*, 2022, Carbonaceous materials from forest waste conversion and their corresponding hazardous pollutants remediation performance, Forests, 13, 2080. https://doi.org/10.3390/f13122080 (Q1 FI 3.282).
2. Article submitted to an ISI Conference Proceeding:
   1. Armanu G.E., Secula M.S., Heipieper H.J., Volf I., 2024, Pseudomonas canadensis immobilized on a carbonaceous material enhance plasticizer biodegradation, Conference Proceedings (ISSN 1314-2704), paper submitted.
3. 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.
   2. Armanu G.E., Volf I., 2022, Natural carriers for bacterial immobilization used in bioremediation, Bulletin of Polytechnic Institute of Iasi, Chemistry and Chemical Engineering section, 68 (72), 3, 109-122.
4. National patent requests:
   1. Stan C.S., Albu C., Volf I., 2024, A lignocellulosic waste valorisation path into a new porous polimeric composite material designed for wastewater treatment, A/00677 din 10.11.2023.
   2. Hristea G., Iordoc M.N., Volf I., 2024, An electroactive carbon material based on lignocellulosic waste for supercapacitors and production process, A /00139 din 28.03.2024.
   3. Volf I., Armanu G.E., Secula M.S., 2024, A natural sustainable carrier for bacterial immobilization used in bioremediation), A /00606 din 11.10.2024.
5. Communications:
   1. Armanu G.E., Tofanica B., 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., Secula M.S., Mamaliga I., Volf I*., 2022, “Predictive carbonaceous materials yields resulted from carbonization 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.T., Secula M.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
   4. 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
   5. 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/
   6. Armanu G.E., Secula M.S., Cimpoeşu N., Volf I., 2024, A biobased nano/micro-structured material for microorganisms immobilization, XXIV^thInternational Multidisciplinary Scientific GeoConference: Surveying, Geology and Mining, Ecology and Management – SGEM 2024, 29 Jun – 8 Jul, https://www.sgem.org/index.php/dates-deadlines/conference-plenary-programme.
   7. Bejenari I., Secula M.S., Volf I., 2024, Integral valorization of biomass waste towards sustainable and value-added hybrid materials, PolyChar World Forum on Advanced Materials, 30th edition, September 11-13. https://icmpp.ro/polychar’30/program.php
   8. Armanu G.E., Secula M.S., Heipieper H.J., Volf I., 2024, Pseudomonas canadensis immobilized on a carbonaceous material enhance plasticizer biodegradation, XXIV^thInternational Multidisciplinary Scientific GeoConference: Surveying, Geology and Mining, Ecology and Management – SGEM 2024, 29 Jun – 8 Jul, https://www.sgem.org/index.php/dates-deadlines/conference-plenary-programme.
   9. Armanu G.E., Bertoldi S., Eberlein C., Heipieper H.J., Secula M.S., Volf I., 2024, Immobilized bacterial cells on a natural carbonaceous material for diethyl phthalate biodegradation, 7th International Conference of the Doctoral School “Gheorghe Asachi” Technical University of Iasi, CSD 2024, May 15-17, https://conferinta-csd.tuiasi.ro/wp-content/uploads/2024/05/Program-CSD2024_full_Updated_12_mai_cover-1.pdf
6. Workshops (11.07.2023; 10.06.2024).
7. Webpage: http://www.cercetare.icpm.tuiasi.ro/proiecte/BIOPOROMAT/2022_en/default.html