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3D Printed Fouling-Resistant Photoactive Membranes for Wastewater Treatment

Periodic Reporting for period 1 - PURAQUA (3D Printed Fouling-Resistant Photoactive Membranes for Wastewater Treatment)

Reporting period: 2022-06-15 to 2024-09-14

The project aimed to address pressing water treatment challenges by developing innovative 3D-printed photocatalytic materials and advanced reactor configurations. Globally, water contamination from hazardous organic pollutants, metals, and pathogens poses significant environmental and health risks, often aggravated by industrial activities. Traditional treatment methods are often insufficient or unsustainable for handling diverse contaminants, necessitating new, cost-effective, and scalable technologies that can be applied in both developed and emerging economies.
PURAQUA project addressed these challenges by (1) developing photoactive catalysts for pollutant degradation and microbial inactivation, (2) creating 3D-printed membranes embedded with these catalysts for water treatment, and (3) designing continuous flow reactors to demonstrate practical applications in water purification.

PROJECT DEVELOPMENTS
1. Development of Photoactive Catalysts: The project has developed TiO2, ZnO, Nb2O₅, and iron oxide-based catalysts, leveraging their unique photocatalytic properties to degrade organic pollutants and eliminate pathogens. By exploring various techniques, including atomic layer deposition and electrophoretic deposition, to immobilize catalysts onto 3D-printed substrates, the project addresses the need for efficient and stable catalyst systems. This focus supports global goals for cleaner water by advancing materials that perform well under irradiation, offering a sustainable solution to water contamination.
2. 3D-Printed Membranes for Water Treatment: By employing advanced materials such as ceramic-like composites, carbon-based inks, and conductor graphene-based substrates, the project has developed membranes capable of degrading contaminants in both batch and continuous flow systems. A circular economy approach is incorporated by using industrial residues like red mud, which enhances sustainability and reduces costs. This objective aligns with the European Union's Green Deal by promoting industrial symbiosis and reducing waste, setting a strong precedent for sustainable manufacturing practices in water treatment.
3. Prototype Development for Continuous Flow Evaluation: The project has created and optimized continuous flow reactors that incorporate these 3D-printed membranes, aiming facilitating large-scale implementation. The design includes both flat and tubular membrane configurations, allowing adaptability for various water treatment needs. This approach underscores the project’s emphasis on scalability and real-world application, vital for addressing water scarcity in urban and industrial contexts.

EXPECTED IMPACTS
While the project introduces innovative approaches in photocatalytic materials and 3D-printed reactor design, its impact is envisioned as a complementary advancement in the field of water treatment. These materials and methods, still in their early stages, may offer incremental improvements to existing water purification technologies by enhancing photocatalytic efficiency and supporting a sustainable materials approach. While not anticipated to replace conventional methods, the project could serve as a building block for further research and development, contributing modestly to cleaner water solutions and potentially influencing sustainable practices in water treatment technologies.
1. RESEARCH OBJECTIVE 1: DEVELOPMENT OF PHOTOACTIVE CATALYSTS
i) TiO2-based Catalysts:
• Investigated immobilization techniques for TiO2 onto 3D-printed substrates, including blending with graphene oxide (GO) ink, in-situ synthesis of TiO2/GO composites, and post-surface modification of carbon nanotubes (CNTs) via atomic layer deposition (ALD).
ii) ZnO-based Catalysts:
• Synthesized ZnO nanoparticles via sol-gel method for incorporation into ceramic-like materials.
• Explored in-situ ZnO synthesis for surface functionalization of 3D-printed ceramic-like materials.
iii) Nb2O5-based Catalysts:
• Prepared Nb2O5 via sol-gel method and optimized thermal treatment for enhanced photocatalytic activity.
• Incorporated Nb2O5 into ceramic-like printable inks.
iv) Iron Oxide-based Catalysts:
• Synthesized hematite and magnetite via co-precipitation for photo-Fenton-like processes.
• Evaluated these materials for bacterial inactivation and virus removal in collaboration with external partners.

2. RESEARCH OBJECTIVE 2: PREPARATION OF 3D-PRINTED MEMBRANES FOR WATER TREATMENT
i) Ceramic-like Materials:
• Developed 3D-printable ceramic-like inks based on alkali-activated aluminosilicate materials.
• Optimized ink composition and printing parameters for desired structural properties.
• Incorporated industrial residues (red mud, biomass fly ash) into the inks, promoting circular economy principles.
• Evaluated the 3D-printed materials for the removal of dyes, hazardous metals, and organic pollutants in both batch and continuous flow systems.
• Incorporated photoactive catalysts (ZnO, Nb2O5) into the inks and investigated their photocatalytic performance.
• Surface-functionalized 3D-printed membranes with CNTs and TiO2 for enhanced catalytic activity.
ii) Carbon-based Materials:
• Developed 3D-printable inks based on graphene derivatives and TiO2 composites.
• Investigated different strategies for TiO2 incorporation, including blending and post-surface deposition.
• Optimized printing parameters and post-treatment processes for improved material properties.
• Explored the use of polyvinyl alcohol (PVA) to enhance the stability of carbon-based materials.
iii) Conductor Graphene-based Materials:
• Utilized FFF to print 3D structures using graphene/PLA filament.
• Surface-modified the 3D-printed structures with TiO2 via electrophoretic deposition (EPD).
• Optimized the EPD process and explored the effect of p-n heterojunctions with NiO.

3. RESEARCH OBJECTIVE 3: DEVELOPMENT OF A PROTOTYPE FOR CONTINUOUS FLOW EVALUATION
i) Designed and fabricated photocatalytic continuous flow reactors for flat and tubular membrane configurations.
ii) Evaluated the performance of 3D-printed membranes in these reactors under various operating conditions.
1. KEY ACHIEVEMENTS:
i) Development of Novel Photocatalysts:
• Successful synthesis of highly efficient Nb2O5 photocatalyst via sol-gel method, optimized through thermal treatment.
• Preparation of ZnO nanoparticles for potential surface modification of 3D-printed materials.
• Synthesis of TiO2 nanoparticles and TiO2/GO composites for photocatalytic applications.
• Development of iron oxide-based photo-Fenton-like catalysts for water disinfection and pollutant removal.
ii) Development of 3D-Printed Photocatalytic Membranes:
• Successful fabrication of 3D-printed ceramic-like membranes incorporating industrial waste (red mud) for sustainable and cost-effective water treatment.
• Optimization of ink formulations and printing parameters to achieve desired structural properties and high porosity.
• Development of 3D-printed graphene-based membranes with immobilized TiO2 photocatalysts for enhanced photocatalytic activity.
• Exploration of surface functionalization techniques (ALD, EPD) for precise control of catalyst deposition and improved catalytic performance.
iii) Development of Novel Photoreactor Configurations:
• Design and fabrication of efficient photocatalytic reactors for flat and tubular membrane geometries.
• Optimization of reactor operating conditions (flow rate, pH, light intensity, wavelength) for enhanced performance.

2. INNOVATIVE APPROACHES:
i) Direct Ink Writing (DIW) of Ceramic-like Materials:
• Formulation of printable ceramic-like inks incorporating industrial residues for sustainable and cost-effective production.
• Optimization of printing parameters to achieve desired structural properties and mechanical performance.
ii) 3D Printing of Carbon-based Materials:
• Development of printable inks based on graphene derivatives and TiO2 composites for enhanced photocatalytic activity.
• Combination of carbon-based materials and metal oxide photocatalysts for enhanced light absorption and charge separation.
• Integration of TiO2 via ALD for improved catalytic performance.
iii) Integration of 3D-Printed Membranes into Reactor Systems:
• Development of proof-of-concept modular reactor designs for practical applications.


3. POTENTIAL IMPACT:
i) Enhanced Water Treatment Technologies:
• Development of efficient and sustainable photocatalytic materials for the removal of emerging contaminants and disinfection of water.
• Innovative 3D printing techniques for the fabrication of customized and high-performance water treatment systems.
• Improved reactor design for enhanced treatment efficiency and reduced energy consumption.
• Improved removal of emerging contaminants and disinfection of water through optimized reactor design and operation.


4. KEY NEEDS FOR FURTHER UPTAKE AND SUCCESS:
i) Scale-up and Commercialization:
• Development of scalable manufacturing processes for 3D-printed photocatalytic materials and reactors.
• Establishment of partnerships with industry to commercialize the technology.
ii) Regulatory Framework and Standardization:
• Development of clear regulatory guidelines for the application of advanced materials and technologies in water treatment.
• Standardization of testing protocols and performance metrics for photocatalytic materials and systems.
iii) Continued Research and Development:
• Further optimization of photocatalyst formulations and 3D printing techniques.
• Investigation of novel reactor configurations and operating conditions.
• Exploration of integration with other water treatment processes for synergistic effects.
• Further optimization of reactor design and operating conditions.