Green MXenes: The Two-Dimensional Materials Forged in Molten Salt

In the quest for powerful new materials, scientists have discovered a safer, greener path to unlocking the potential of MXenes.

Green Chemistry Materials Science Nanotechnology

What Are MXenes and Why Do They Matter?

MXenes (pronounced "max-eens") are a family of two-dimensional materials made from transition metal carbides, nitrides, or carbonitrides that combine exceptional properties with versatile applications.

Layered Structure

MXenes have a fascinating layered structure represented by the formula Mn+1XnTx, where:

  • M stands for early transition metals like titanium, vanadium, or molybdenum
  • X represents carbon or nitrogen
  • Tx indicates surface functional groups such as oxygen (-O), hydroxyl (-OH), or halogens like chlorine (-Cl) 1 7

Exceptional Properties

What makes MXenes extraordinary is their unique combination of properties:

  • Exceptional electrical conductivity 2 3
  • Superior mechanical strength 2 3
  • Natural hydrophilicity (water-attracting) 2 3
  • High surface area 2 3

MXene Applications

Energy Storage

Batteries and supercapacitors 3 8

Water Purification

Membranes and filters 3 8

EMI Shielding

Electromagnetic interference protection 3 8

Biomedical

Sensors and drug delivery 3 8

The Problem With Conventional MXene Synthesis

Health & Environmental Hazards

HF is extremely corrosive and poisonous. Fluoride ions can penetrate body tissues, causing potentially fatal damage with prolonged exposure 1 4 .

Undesirable Surface Chemistry

HF-based etching introduces fluorine terminations that negatively impact electrical conductivity and limit performance 1 4 6 .

Material Stability Issues

Harsh etching conditions create excessive defects, making MXenes more vulnerable to oxidation and degradation over time 1 .

These limitations prompted researchers worldwide to ask a critical question: Could we create MXenes through a safer, more sustainable process that also enhances their performance?

The Green Revolution: Lewis Acidic Molten Salt Etching

In 2019, a breakthrough emerged: the Lewis acid molten salt (LAMS) method, a fluoride-free approach that addresses the shortcomings of traditional MXene synthesis 1 5 .

This innovative technique involves heating metal halides like CuCl₂, NiCl₂, or ZnCl₂ until they melt into a liquid salt bath. When MAX phase powder is added, the more reactive metal in the molten salt displaces the "A" element from the MAX phase 1 5 .

Replacement Reaction
MAX phase + Metal halide salt → MXene + Byproduct metal + New salt compound

Example with Ti₃C₂Clₓ MXene:

Ti₃AlC₂ + CuCl₂ → Ti₃C₂Clₓ + Cu + AlCl₃

Why Molten Salt Etching Represents a Game Changer

Eco-Friendly and Safe

By eliminating fluorine-based chemicals, the process removes the risks of HF exposure and toxic waste generation 5 .

Superior Surface Control

It enables uniform coverage with halogen terminations, which can enhance electrochemical performance 1 .

Expanded MXene Family

The method allows access to previously hard-to-synthesize MXenes from MAX phases with "A" elements beyond aluminum 1 .

Scalability

The simpler, safer process opens the door to industrial-scale MXene production 5 .

Diverse Termination Options

By choosing different metal halide salts, researchers can create MXenes with -Cl, -Br, -I, or mixed halogen terminations 1 9 .

Enhanced Performance

Halogen-terminated MXenes often show improved electrical conductivity and stability compared to fluoride-terminated ones.

A Closer Look: The Ti₃C₂Cl₂ Breakthrough Experiment

Methodology: Step-by-Step

Preparation

Researchers placed anhydrous copper(II) chloride (CuCl₂) powder and Ti₃AlC₂ MAX phase powder in a ceramic crucible at a 4:1 molar ratio 1 5 .

Heating Phase

The crucible was transferred to a tube furnace, sealed and purged with argon gas. The temperature was increased to 750°C and maintained for 5 hours 5 .

Cooling and Collection

After reaction, the system was slowly cooled to room temperature, producing MXene along with metallic copper and salt byproducts.

Purification

Copper byproduct was removed with ammonium persulfate solution, and excess salts were dissolved and washed away 5 .

Results and Significance

The experiment successfully produced high-quality, chlorine-terminated Ti₃C₂Cl₂ MXene with remarkable characteristics:

Excellent Structural Integrity: The MXene maintained its layered structure without significant defects or oxidation.
Uniform Surface Termination: Chlorine atoms consistently covered the surface, providing predictable chemical behavior.
Superior Electrochemical Properties: The material demonstrated outstanding performance in energy storage applications.

Perhaps most impressively, the surface chemistry could be further modified. By treating Ti₃C₂Cl₂ with tetrabutylammonium hydroxide, researchers transformed it from a hydrophobic material (water contact angle of 136°) to a hydrophilic one (contact angle decreasing to 23°) 1 .

Comparison of MXene Synthesis Methods

Traditional HF Etching vs. Molten Salt Etching
Property HF Etching Molten Salt Etching
Surface Terminations Mixed -F, -O, -OH Uniform -Cl, -Br, -I
Safety Concerns High (toxic, corrosive) Low (halogen salts)
Environmental Impact Significant (toxic waste) Minimal (recyclable salts)
Electrical Conductivity Limited by -F groups Enhanced by halogen groups
Hydrophobicity Hydrophilic Tunable (hydrophobic possible)
Electrochemical Performance in 3M H₂SO₄ Electrolyte
MXene Type Surface Group Specific Capacity
Ti₃C₂Cl₂ -Cl 102 C/g
Ti₃C₂Br₂ -Br 34 C/g
Ti₃C₂I₂ -I 70 C/g
Conventional MXene Mixed -F/-O/-OH ~50-80 C/g

The Scientist's Toolkit: Key Reagents in Molten Salt MXene Synthesis

Reagent Function Examples & Notes
MAX Phase Precursors Source material for MXenes Ti₃AlC₂, Ti₂AlC, V₂AlC; determines the M and X elements in the final MXene
Metal Halide Salts Lewis acidic etchants in molten state CuCl₂, ZnCl₂, NiCl₂, FeCl₂, AgCl; choice of salt determines termination groups
Inert Gas Creates oxygen-free environment Argon or nitrogen; prevents oxidation during high-temperature reaction
Oxidizing Solutions Removes metallic byproducts Ammonium persulfate; dissolves elemental copper without damaging MXene
Washing Solvents Purifies final product Deionized water, ethanol, HCl; removes salt residues and impurities

Beyond the Lab: Applications and Future Outlook

Energy Storage

Halogen-terminated MXenes demonstrate exceptional performance in lithium-ion batteries, sodium-ion batteries, and supercapacitors 5 . Their tunable surface chemistry enables faster charging and higher energy density.

Environmental Remediation

MXenes show promise in water purification membranes, heavy metal removal, and catalytic degradation of pollutants 2 3 . The fluoride-free synthesis makes them more compatible with sustainable applications.

Electronics & Communications

MXenes' exceptional electrical conductivity makes them ideal for electromagnetic interference shielding, transparent conductive films, and sensors 8 .

Future Directions

Solvent-Free Gas-Phase Etching

Researchers are exploring methods that could simplify production even further 9 .

Electrochemical Approaches

These methods offer precise control over termination groups 4 .

The Future is Green

As these methods mature, we can expect MXenes to become more accessible and affordable, accelerating their integration into commercial technologies and accelerating our transition to sustainable energy solutions.

A Greener Path to Advanced Materials

The development of fluoride-free molten salt etching represents more than just a technical improvement in materials synthesis—it embodies a fundamental shift toward sustainable nanotechnology.

By replacing hazardous chemicals with safer alternatives, researchers have not only made MXene production more environmentally friendly but have also unlocked new performance capabilities through precise control of surface chemistry.

As we stand at the forefront of this materials revolution, the story of green MXene synthesis offers a powerful lesson: the most advanced technologies need not come at an environmental cost. Through clever chemistry and innovative thinking, we can develop sustainable pathways to the materials that will power our future.

References

This article was based on recent scientific advancements in MXene research. For those interested in exploring further, the references provide additional technical details and context.

References