Gas Adsorption Phenomena in Graphene-Based Systems

Graphene’s atomically thin two-dimensional structure combines exceptionally high surface area with tunable electronic properties, making it a compelling platform for gas adsorption studies. Gas molecules interact with pristine graphene predominantly through weak van der Waals forces, a process known as physisorption, which can be enhanced or supplanted by stronger chemical bonds in chemisorption when dopants or functional groups are introduced. Tailoring graphene via heteroatom doping, vacancy creation or surface functionalisation alters the local electronic density of states, modulating adsorption energies, charge transfer and sensor response. These engineered interactions underpin applications in gas storage, separation, catalysis and sensing. In sensing, minute adsorption-induced changes in conductivity or optical response enable detection of target species at low concentrations. In energy storage and environmental remediation, adsorption capacity and reversibility determine performance. Understanding the fundamental thermodynamics and kinetics of adsorption and desorption on various graphene architectures—including nanoribbons, capsules and hybrid heterostructures—is essential for the rational design of next-generation devices for global challenges in clean energy, pollution monitoring and chemical processing.

Research from Nature Portfolio

Phosphorus-doped tetragonal graphene nanocapsules have been shown to exhibit markedly different affinities for ozone and sulphur dioxide. The novel sp²-carbon allotrope undergoes structural deformation upon gas binding, with calculated adsorption energies reaching –4.34 eV for O₃ and –0.30 eV for SO₂ in the doped system. Charge-density analyses reveal pronounced covalent character in O₃ interactions and significant modulation of the electronic bandgap and optical absorption spectra, pointing to dual electrical and optical sensing modalities. Thermodynamic assessment indicates that O₃ adsorption is exothermic and spontaneous, whereas SO₂ attachment is endothermic, underscoring selectivity control via dopant chemistry. Temperature-programmed terahertz emission measurements have quantified the adsorption energy of oxygen molecules on graphene at approximately 0.15 eV, resolving longstanding theoretical disputes. The study visualises spatial distributions of adsorbed O₂ during thermal desorption, elucidating the microscopic mechanisms governing physisorption on atomically layered surfaces. These insights provide a benchmark for the interaction strength of small diatomic gases with pristine graphene and help calibrate models for gas‐driven property modulation in two-dimensional materials.

Gas Adsorption Phenomena in Graphene-Based Systems publication trend

The graph below shows the total number of articles in gas adsorption phenomena in graphene-based systems across all publications each year (not limited to Nature Index journals).

Technical terms

Adsorption energy: The energy change when a gas molecule binds to a surface, indicating interaction strength.

Physisorption: Reversible gas binding via weak van der Waals forces without significant charge redistribution.

Chemisorption: Formation of chemical bonds between adsorbate and surface, often involving charge transfer and surface reconstruction.

Charge transfer: The movement of electron density between graphene and an adsorbed molecule, affecting electronic properties.

Density of states (DOS): The number of electronic states at each energy level, used to assess how adsorption modifies electronic structure.

References

1. Density functional theory study of B‐ and Si‐doped carbons and their adsorption interactions with sulfur compounds. Carbon Energy (2024).
2. Performance of Intrinsic and Modified Graphene for the Adsorption of H2S and CH4: A DFT Study. Nanomaterials (2020).
3. Recent Developments in Graphene-Based Toxic Gas Sensors: A Theoretical Overview. Sensors (2021).
4. Adsorption energy of oxygen molecules on graphene and two-dimensional tungsten disulfide. Scientific Reports (2017).
5. Phosphorus-doped T-graphene nanocapsule toward O3 and SO2 gas sensing: a DFT and QTAIM analysis. Scientific Reports (2024).