Periodic Reporting for period 1 - SAFARI (SAFE AND SUSTAINABLE BY DESIGN GRAPHENE/MXENES HYBRIDS)
Berichtszeitraum: 2023-12-01 bis 2025-05-31
The SAFARI project is an integral venture aimed at responsibly advancing 2D materials from lab-scale to impactful applications, such as biosensors, conductive inks, and electromagnetic shielding technologies.
Overall Objectives:
1.2D material manufacturing and characterization with SSbD profiles:
a.Scaling Up sustainable MAX Phase and MXene production to TRL 5
b.Functionalizing and hybridizing MXenes with graphene and integration into target applications
c.Comprehensive materials characterization along the supply chain and leverage In-Silico predictive tools to correlate 2D material properties with SSbD profiles
2.Establish and implement a Safe and Sustainable by Design (SSbD) strategy
a.Build a robust toxicity and ecotoxicity assessment methodology for 2D materials
b.Develop an iterative SSbD strategy uniting predictive and experimental approaches
c.Embed SAFARI characterization profiles into digital Safe-by-Design infrastructure
3.Maximize impact through exploitation, dissemination, and communication
a.Foster awareness and knowledge exchange across diverse stakeholder groups
b.Promote and monitor intellectual property (IP)
c.Build exploitation roadmaps withing the Graphene Flagship Initiative
Overall Objectives:
1.2D material manufacturing and characterization with SSbD profiles:
a.Scaling Up sustainable MAX Phase and MXene production to TRL 5
b.Functionalizing and hybridizing MXenes with graphene and integration into target applications
c.Comprehensive materials characterization along the supply chain and leverage In-Silico predictive tools to correlate 2D material properties with SSbD profiles
2.Establish and implement a Safe and Sustainable by Design (SSbD) strategy
a.Build a robust toxicity and ecotoxicity assessment methodology for 2D materials
b.Develop an iterative SSbD strategy uniting predictive and experimental approaches
c.Embed SAFARI characterization profiles into digital Safe-by-Design infrastructure
3.Maximize impact through exploitation, dissemination, and communication
a.Foster awareness and knowledge exchange across diverse stakeholder groups
b.Promote and monitor intellectual property (IP)
c.Build exploitation roadmaps withing the Graphene Flagship Initiative
Main achievements regarding 2D material manufacturing and functionalization as well as the development of a Safe and Sustainable by Design (SSbD) strategy are summarized below:
MAX and Mxene phase manufacturing: Thermal modeling using ANSYS led to the design and fabrication of optimized sintering tools for large-volume MAX phase synthesis. This enabled successful production of an 800-gram batch. Futhermore, the scalable HEBM-SPS method offers potential for diverse MAX phase compositions.
A novel pilot-scale laboratory production line was developed for Ti₃C2 MXene synthesis using combined low-power microwaves and high-frequency bulk acoustic waves (BAW), completely avoiding toxic hydrofluoric acid etchants. This physical etching method reduced MXene production time dramatically to about 6 hours. Also, Cr2C MXene synthesis was demonstrated using high-frequency acoustic emission and chemical digestion. Alternative synthesis methods were also explored, including a molten salt synthesis using a NaCl/KCl eutectic with CuCl2.Produced MXenes demonstrated excellent pseudo-capacitance and electrochemical performance.
MXene functionalization and Characterization of 2D Materials: Functionalization experiments on Ti₃C2Tₓ MXenes (primarily those produced by etching) with various organic molecules and polymers including PVA, PS, PPy, APTES, and other organic compounds. Results demonstrate successful grafting of PVA onto Ti₃C2Tₓ, with potential functionalization by PS and PPy as well. Also, surface decoration of Ti₃C2Tₓ MXenes with copper nanoparticles (Cu NPs) was achieved.DFT-based computational studies were carried out on pristine and functionalized Ti₃C2 MXenes. Functional groups (F, O, OH) were modeled at different surface sites, revealing preferential binding and slight structural deformation consistent with experiments. Results closely matched experimental XRD data and confirmed the metallic conductivity of MXenes, with Ti atoms identified as key contributors to charge density.
Safe and Sustainable by Design (SSbD) Strategy: A decision tree based on the SSbD framework was developed to classify materials by hazard level. Ti₃C2 Mxenes were tested using standardized dispersion protocols on lung and liver cell models under 2D and advanced 3D static and dynamic culture conditions. Results showed enhanced physiological relevance and dose-dependent toxicity in 3D models compared to 2D cultures and most materials ranked as safe or requiring standard safety measures. Risk prioritization combining ecotoxicological and toxicological endpoints was studied.
Worker exposure and occupational risk was assessed. Qualitative and quantitative evaluation of worker exposure to airborne nanomaterials during MAX phase and MXene synthesis and functionalization were carried out. Data informed risk control recommendations emphasizing engineering, administrative, and personal protective measures tailored to process specifics.
In Silico Toxicological Profiling: Computational analyses modeled MXene nanoparticle interactions with human proteins and lipid membranes. A database of nanoparticle structures was created and coupled with human metabolic proteins, revealing weak but consistent surface interactions, primarily avoiding active site binding. Membrane permeability studies demonstrated nanoparticles do not cross lipid bilayers.
MAX and Mxene phase manufacturing: Thermal modeling using ANSYS led to the design and fabrication of optimized sintering tools for large-volume MAX phase synthesis. This enabled successful production of an 800-gram batch. Futhermore, the scalable HEBM-SPS method offers potential for diverse MAX phase compositions.
A novel pilot-scale laboratory production line was developed for Ti₃C2 MXene synthesis using combined low-power microwaves and high-frequency bulk acoustic waves (BAW), completely avoiding toxic hydrofluoric acid etchants. This physical etching method reduced MXene production time dramatically to about 6 hours. Also, Cr2C MXene synthesis was demonstrated using high-frequency acoustic emission and chemical digestion. Alternative synthesis methods were also explored, including a molten salt synthesis using a NaCl/KCl eutectic with CuCl2.Produced MXenes demonstrated excellent pseudo-capacitance and electrochemical performance.
MXene functionalization and Characterization of 2D Materials: Functionalization experiments on Ti₃C2Tₓ MXenes (primarily those produced by etching) with various organic molecules and polymers including PVA, PS, PPy, APTES, and other organic compounds. Results demonstrate successful grafting of PVA onto Ti₃C2Tₓ, with potential functionalization by PS and PPy as well. Also, surface decoration of Ti₃C2Tₓ MXenes with copper nanoparticles (Cu NPs) was achieved.DFT-based computational studies were carried out on pristine and functionalized Ti₃C2 MXenes. Functional groups (F, O, OH) were modeled at different surface sites, revealing preferential binding and slight structural deformation consistent with experiments. Results closely matched experimental XRD data and confirmed the metallic conductivity of MXenes, with Ti atoms identified as key contributors to charge density.
Safe and Sustainable by Design (SSbD) Strategy: A decision tree based on the SSbD framework was developed to classify materials by hazard level. Ti₃C2 Mxenes were tested using standardized dispersion protocols on lung and liver cell models under 2D and advanced 3D static and dynamic culture conditions. Results showed enhanced physiological relevance and dose-dependent toxicity in 3D models compared to 2D cultures and most materials ranked as safe or requiring standard safety measures. Risk prioritization combining ecotoxicological and toxicological endpoints was studied.
Worker exposure and occupational risk was assessed. Qualitative and quantitative evaluation of worker exposure to airborne nanomaterials during MAX phase and MXene synthesis and functionalization were carried out. Data informed risk control recommendations emphasizing engineering, administrative, and personal protective measures tailored to process specifics.
In Silico Toxicological Profiling: Computational analyses modeled MXene nanoparticle interactions with human proteins and lipid membranes. A database of nanoparticle structures was created and coupled with human metabolic proteins, revealing weak but consistent surface interactions, primarily avoiding active site binding. Membrane permeability studies demonstrated nanoparticles do not cross lipid bilayers.
Integrated Framework for MAX Phase and MXene Manufacturing, Functionalization, Multi-Modal Characterization, and Computational Modeling
This integrated approach combining advanced manufacturing, green and scalable synthesis, functionalization, structural and electrochemical characterization, and state-of-the-art computational modeling significantly advances the fundamental understanding and technological readiness of MAX phases and MXenes. Novel pilot-scale manufacturing innovations reduce hazardous reagents and dramatically shorten production times, enhancing safety and sustainability toward commercialization. Functionalization strategies and hybrid material development open new application avenues in energy storage, catalysis, biosensors, electronics, EMI shielding, additive manufacturing, and nuclear energy.
Integrated Framework of In Vitro and In Silico Toxicity Assessment
This comprehensive, multiscale assessment combining experimental in vitro toxicology, ecotoxicology, occupational exposure analysis, and advanced computational modeling significantly advances the safety evaluation of MXene nanomaterials. Used methods support the Safe and Sustainable by Design (SSbD) framework by enabling more precise hazard identification and risk prioritization. Worker exposure data inform targeted risk management enhancing occupational health during MXene production and processing. In silico approaches provide predictive tools that can reduce reliance on extensive in vitro or in vivo testing. These integrated efforts underpin the development of safer MXene materials and inform regulatory guidance and industrial best practices, thereby accelerating sustainable innovation in 2D nanomaterial technologies.
This integrated approach combining advanced manufacturing, green and scalable synthesis, functionalization, structural and electrochemical characterization, and state-of-the-art computational modeling significantly advances the fundamental understanding and technological readiness of MAX phases and MXenes. Novel pilot-scale manufacturing innovations reduce hazardous reagents and dramatically shorten production times, enhancing safety and sustainability toward commercialization. Functionalization strategies and hybrid material development open new application avenues in energy storage, catalysis, biosensors, electronics, EMI shielding, additive manufacturing, and nuclear energy.
Integrated Framework of In Vitro and In Silico Toxicity Assessment
This comprehensive, multiscale assessment combining experimental in vitro toxicology, ecotoxicology, occupational exposure analysis, and advanced computational modeling significantly advances the safety evaluation of MXene nanomaterials. Used methods support the Safe and Sustainable by Design (SSbD) framework by enabling more precise hazard identification and risk prioritization. Worker exposure data inform targeted risk management enhancing occupational health during MXene production and processing. In silico approaches provide predictive tools that can reduce reliance on extensive in vitro or in vivo testing. These integrated efforts underpin the development of safer MXene materials and inform regulatory guidance and industrial best practices, thereby accelerating sustainable innovation in 2D nanomaterial technologies.