Zirconium-modified sol-gel magnetic hybrid materials for advanced heavy metal removal from wastewater (zirmagsolgel)

PN-IV-P7-7.1-PED-2024-1069


Pollution with heavy metals, such as As, Pb, and Cr, has harmful effects on humans and the ecosystem by reducing the amount of drinking water. Zirconium adsorbent materials are effective in reducing the impact of water pollution. The use of these materials as polymer composites has proven beneficial, enabling multiple decontamination cycles.

PROJECT OBJECTIVE

The ZIRMAGSOLGEL project aims to develop hybrid magnetic sol-gel materials modified with zirconium (SGMPs-Zr). Therefore, not only is a combination of adsorbent and magnetic properties achieved, but magnetic separation also becomes possible. In hybrid materials, which contain both organic and inorganic phases, an essential factor is the compatibility between the components. Thus, in the first stage, research will aim to obtain hybrid materials with silane groups and magnetite content (SGMPs), specifically by developing recipes that ensure a uniform distribution of magnetite in the organic matrix. Subsequently, the modification stage with zirconium can proceed.

The validation of the new hybrid materials will be achieved through tests, initially performed on synthetic waters containing known levels of the targeted heavy metals. In the next stage, real contaminated waters will be tested.

The project’s feasibility is supported by the skills of the two partners involved: ICECHIM – advanced knowledge in the synthesis of hybrid materials and the sol-gel process; and EDAS-EXIM S.R.L. – complementary knowledge of specific water quality analyses

RESULTS

The key results of the project consist of experimental models of hybrid materials with silane groups and magnetite content (SGMPs) and validation of the innovative laboratory technology for obtaining hybrid materials modified with zirconium (SGMPs-Zr); Laboratory protocol for testing contaminated waters;

  • 1 patent application
  • 3 WoS indexed articles
  • 5 scientific communications and the project website, where the progress of the project can be followed

Project funded by the Executive Unit for Financing Higher Education, Research, Development and Innovation UEFISCDI.

Project duration (24 months): 03.01.2025-31.12.2026

Project Budget from UEFISCDI: 750.000 lei

Co-fund EDAS-EXIM SRL: 150.000 lei

Project Director (ICECHIM): Dr. Sandu Teodor

Project Responsible (EDAS): Dr. Olaru Andreea

STAGE I- 2025

Industrial research on the formulated concept of the technology to obtain hybrid materials containing magnetic particles through sol-gel processes (Sol-Gel Magnetic Particles-SGMPs) and hybrid materials of SGMPs type modified with zirconium (SGMPs-Zr). Studies on the efficiency of using zirconium in the remediation of waters contaminated with the targeted heavy metals

OBJECTIVES

The main objective is to develop a demonstration experimental model for the production of hybrid materials with magnetic properties and zirconium modification, via the sol-gel process, capable of advanced removal of targeted heavy metals (arsenic, lead and chromium).

A 1.1. Industrial research on obtaining hybrid materials containing magnetic particles through sol-gel processes (SGMPs)

A 1.2. Industrial research on obtaining PET-DA oligomeric structures

A 1.3. Preliminary tests to determine the effectiveness of zirconium in decontamination of synthetic waters containing the targeted heavy metals

A 1.4. Establishing test protocols for the hybrid materials that will be developed

A 1.5. Demonstration of the functionality and validation of the technology for obtaining SGMPs

A 1.6. Development of laboratory technology for obtaining SGMPs-Zr

A 1.7. Validation of the technology for obtaining SGMPs-Zr

A 1.8. Dissemination of results

SUMMARY OF STAGE I

The ZIRMAGSOLGEL project aims to develop a technology for the production of innovative hybrid materials, namely zirconium-modified Sol-Gel Magnetic particles (SGMP-Zr), which are highly efficient at purifying waters contaminated with heavy metals, such as arsenic, lead, and chromium. Elements of originality: (i) integrating the magnetic component (magnetite, Fe3O4) for the first time into a sol-gel network, resulting in Sol-Gel Magnetic Particles (SGMP); (ii) subsequent modification of SGMP particles with zirconium, with the formation of SGMP-Zr; (iii) the synergistic combination of the adsorption properties of zirconium with the porosity of sol-gel materials, with a possitive effect on the efficiency of decontamination; (iv) the possibility of recovering the spent adsorbent in a magnetic field. The magnetic particles were produced using different precursors and experimental variants (flask vs. reactor), with or without a surfactant.

The SGMP-Zr and reference samples (MP, SGMP) were characterized for chemical structure (FTIR), morphology and chemical composition (SEM-EDX), particle size (DLS), and porosity (BET). The FTIR spectra confirm the success of the SGMP preparation, through characteristic peaks for both SG (Si-O and N-H bonds) and magnetite (Fe-O), and the success of the modification with Zr, through the formation of the Si-O-Zr bond. Also, the SEM images confirm the success of both magnetite modification stages: with silane groups and with Zr; the latter produces more significant morphological changes. At the same time, the EDX spectra indicate the presence of Zr after the second modification, which also correlates with changes in particle size (DLS), the largest sizes corresponding to the samples modified with Zr.

Modification with silane moieties decreases the BET and pore surface areas, whereas Zr modification increases them. Within the CO partner’s activity, diamines were prepared from PET, with recycling carried out simultaneously with the development of compounds that can be used later. The EDAS-EXIM SRL partner developed a protocol for obtaining synthetic waters with known concentrations of the targeted heavy metals and for testing the decontamination efficiency of the innovative materials under the project. It was found that all samples achieve good decontamination, but samples containing magnetite prepared in the reactor are more efficient.

It is noteworthy that zirconium significantly improves the process performance. XRF analyses of solid samples in contact with contaminated water indicated retention of heavy metals in the material, especially in samples containing Zr. The objectives within Stage 1/2025 were fully achieved, with 100% compliance.

RESULTS

The results obtained within Stage I/2025 are consistent with the project objectives and the result indicators proposed for Stage 1:

  • Experimental models of SGMP and SGMPs-Zr production technologies;
  • Laboratory protocol for testing contaminated water;
  • 6 communications within international and national conferences;
  • 1 ISI article published;
  • Project web page creation.

The summary and results of Stage I/2025 are accessible on the ZIRMAGSOLGEL project website, Contract 18PED/2025: Romanian language https://icechim.ro/project/zirmagsolgel-ro/ and English language https://icechim.ro/project/zirmagsolgel-en/. The project website contains the project scope and specific objectives, estimated results, and achieved indicators.

DISSEMINATION

Harnessing research results by publishing an ISI article and attending 6 dedicated scientific events exceeds the proposed achievement indicators (2 scientific communications and 1 ISI article submitted):

I. Articles

1. T. Sandu, A. L. Chiriac, A. Zaharia, T. V. Iordache, A. Sârbu, New Trends in Preparation and Use of Hydrogels for Water Treatment, Gels 2025, 11, 238 (Q1).

II. Conferences

1. T. Sandu, S. V. Dolana, A. Sârbu, E. B. Stoica, A. M. Pană, A. L. Chiriac, A. Zaharia, D. G. Mitrea, I. Atkinson. B. Tsyntsarski, G. Georgiev, Comparison of different methods for delivering spherical magnetic properties, Twelfth National Conference on Chemistry, University of Chemical Technology and Metallurgy, 25-26.09.2025, Sofia, Bulgaria

2. T. Sandu, T. V. Iordache, A. Sârbu, E. B. Stoica, S. V. Dolana, A. G. Olaru, Zirconium- Modified Sol-Gel Hybrid Materials for Advanced Heavy Metal Removal from Wastewater- ZIRMAGSOLGEL, Festival of Innovation and Technological Transfer, November 17th – 20th, 2025, Târgoviște, România (Diploma și Medalia de Aur în cadrul manifestării)

3. A. Sârbu, M. V. Dumitru, A. L. Neagu, A. Zaharia, T. Sandu, O. Pavel, T. V. Iordache, R. Zăvoianu, Hidrogeluri compozite cu rețea semi-interpenetrată și cu

HDL, pentru eliberarea controlată a unui fitoextract de topinambur, A XX-a ediţie a conferinţei internaţionale “Zilele Academiei de Științe Tehnice din România – 2025” (ZASTR-2025), cu tema, Energia și materia în industria modernă, organizată la Universitatea „Dunărea de Jos” din Galați, 18-19.09.2025, Galați, România.

4. M. V. Iordănescu (Dumitru), T. V. Iordache, I. C. Gîfu, A. M. Gavrilă, A. L. Chiriac, A. Zaharia, A. Sârbu, S. V. Dolana, I. E. Neblea, T. Sandu, Polymer Membranes Modified with Silanol Moieties, Simpozionul Internațional Prioritățile Chimiei pentru o Dezvoltare Durabilă

(PRIOCHEM XXI), 15- 17.10.2025, București, România

5. E. B. Stoica, A. L. Chiriac, A. Zaharia, S. V. Dolana, N. Stănică, T. V. Iordache, A. Sârbu, A. G. Olaru, T. Sandu, Polymer Composites Endowed with Magnetic Features, Simpozionul Internațional Prioritățile Chimiei pentru o Dezvoltare Durabilă (PRIOCHEM XXI), 15- 17.10.2025, București, România.

6. S. V. Dolana, T. V. Iordache, T. Sandu, A. Zaharia, I. E. Neblea, E. B. Stoica, A. Ficai, PET Derived Polyamines for Foams based on Aza- Michael Reaction, Applications of Chemistry in nanosciences and Biomaterials Engineering, NanoBioMat2025- Winter Edition, 26-28.11, București, România.