Gas Molecules Research Articles

Experimental Insights into the Formation, Reactivity, and Crosstalk of Thionitrite (SNO−) and Perthionitrite (SSNO−)

AbstractHydrogen sulfide (H2S) and nitric oxide (NO) are important gaseous biological signaling molecules that are involved in complex cellular pathways. A number of physiological processes require both H2S and NO, which has led to the proposal that different H2S/NO⋅ crosstalk species, including thionitrite (SNO−) and perthionitrite (SSNO−), are responsible for this observed codependence. Despite the importance of these S/N hybrid species, the reported properties and characterization, as well as the fundamental pathways of formation and subsequent reactivity, remain poorly understood. Herein we report new experimental insights into the fundamental reaction chemistry of pathways to form SNO− and SSNO−, including mechanisms for proton‐mediated interconversion. In addition, we demonstrate new modes of reactivity with other sulfur‐containing potential crosstalk species, including carbonyl sulfide (COS).

Hydrogen Sulfide‐Triggered Artificial DNAzyme Switches for Precise Manipulation of Cellular Functions

AbstractThe development of synthetic molecular tools responsive to biological cues is crucial for advancing targeted cellular regulation. A significant challenge is the regulation of cellular processes in response to gaseous signaling molecules such as hydrogen sulfide (H2S). To address this, we present the design of Gas signaling molecule‐Responsive Artificial DNAzyme‐based Switches (GRAS) to manipulate cellular functions via H2S‐sensitive synthetic DNAzymes. By incorporating stimuli‐responsive moieties to the phosphorothioate backbone, DNAzymes are strategically designed with H2S‐responsive azide groups at cofactor binding locations within the catalytic core region. These modifications enable their activation through H2S‐reducing decaging, thereby initiating substrate cleavage activity. Our approach allows for the flexible customization of various DNAzymes to regulate distinct cellular processes in diverse scenarios. Intracellularly, the enzymatic activity of GRAS promotes H2S‐induced cleavage of specific mRNA sequences, enabling targeted gene silencing and inducing apoptosis in cancer cells. Moreover, integrating GRAS with dynamic DNA assembly allows for grafting these functional switches onto cell surface receptors, facilitating H2S‐triggered receptor dimerization. This extracellular activation transmits signals intracellularly to regulate cellular behaviors such as migration and proliferation. Collectively, synthetic switches are capable of rewiring cellular functions in response to gaseous cues, offering a promising avenue for advanced targeted cellular engineering.

Improved gas sensing properties of copper-doped MoSe2 monolayers: a first-principles study on CO2 and NO2 adsorption

Abstract This paper investigates the impact of copper (Cu)-doped MoSe2 monolayer (ML) on gas sensing properties. The adsorption behaviour of CO2 and NO2 gas molecules on Cu-doped MoSe2 ML is reported and various sensing and electronic parameters such as adsorption energy, charge transfer and recovery time, are computed to delineate the adsorption characteristics and gas sensitivity. In our study, the doped Cu-atom in Se vacant MoSe2 ML shows the adsorption energies to be −1.32 eV (O-orient) and −1.72 eV (C-orient), for CO2, while for NO2, they are −0.879 eV (O-orient) and −1.06 eV (N-orient), respectively. The negative formation energy of −6.62 eV shows the electronic stability of Cu-doped MoSe2 ML and thermal stability, demonstrated by the molecular dynamics study through the Nose-Vervlet Thermostat (NVT) algorithm. Also, significant changes are observed in electronic conductivity and work function upon adsorbed Cu-MoSe2 ML. Lastly, these outcomes illustrate that Cu doping amplifies the capture ability of MoSe2 ML towards gas molecules, fostering improved electron interaction between the substrate surface and gas molecules, consequently enhancing its gas sensing ability.

One‐Pot Synthesis of 2‐Substituted‐4,5‐dimethyloxazoles from Amides and Acetylene Gas in the KOH/MeOH/DMSO Catalytic Triad

AbstractPharmaceutically prospective 2‐substituted‐4,5‐dimethyloxazoles are synthesized in 16–58% yield via cascade assembly of one molecule of primary amide with two molecules of acetylene gas in the KOH/MeOH/DMSO catalytic triad (90 °C, 2 h). This self‐organization of oxazoles demonstrates unexpected successful competition with the alkaline hydrolysis of amides. The mechanism involving amide N‐vinylation, enamine‐imine isomerization, imine ethynylation and intramolecular O‐vinylation cascade sequence has been deduced and supported by quantum‐chemical calculations using the B2PLYP−D3/6‐311+G**//B3LYP/6‐31+G*+IEF PCM (B3LYP/6‐31+G*) approach.

Theoretical Study of the Magnetic Mechanism of a Pca21 C4N3 Monolayer and the Regulation of Its Magnetism by Gas Adsorption

For metal-free low-dimensional ferromagnetic materials, a hopeful candidate for next-generation spintronic devices, investigating their magnetic mechanisms and exploring effective ways to regulate their magnetic properties are crucial for advancing their applications. Our work systematically investigated the origin of magnetism of a graphitic carbon nitride (Pca21 C4N3) monolayer based on the analysis on the partial electronic density of states. The magnetic moment of the Pca21 C4N3 originates from the spin-split of the 2pz orbit from special carbon (C) atoms and 2p orbit from N atoms around the Fermi energy, which was caused by the lone pair electrons in nitrogen (N) atoms. Notably, the magnetic moment of the Pca21 C4N3 monolayer could be effectively adjusted by adsorbing nitric oxide (NO) or oxygen (O2) gas molecules. The single magnetic electron from the adsorbed NO pairs with the unpaired electron in the N atom from the substrate, forming a Nsub-Nad bond, which reduces the system’s magnetic moment from 4.00 μB to 2.99 μB. Moreover, the NO adsorption decreases the both spin-down and spin-up bandgaps, causing an increase in photoelectrical response efficiency. As for the case of O2 physisorption, it greatly enhances the magnetic moment of the Pca21 C4N3 monolayer from 4.00 μB to 6.00 μB through ferromagnetic coupling. This method of gas adsorption for tuning magnetic moments is reversible, simple, and cost-effective. Our findings reveal the magnetic mechanism of Pca21 C4N3 and its tunable magnetic performance realized by chemisorbing or physisorbing magnetic gas molecules, providing crucial theoretical foundations for the development and utilization of low-dimensional magnetic materials.

Theoretically design of 2D penta-BN2/penta-Graphene wdW heterostructure for NO gas sensing implications: a first-principles study

As air pollution becomes more and more serious, the detection of harmful gas of NO has become an urgent need in daily life. In this paper, the electronic and gas-sensing properties of penta-BN2/penta-Graphene heterojunction (P-BN2/P-G) are studied by density functional theory and non-equilibrium Green's function method. The analysis results indicate that the P-BN2/P-G heterojunction has metallic properties. The electronic structures in combination with the adsorption behavior shows that the P-BN2/P-G heterojunction can chemically adsorb NO gas molecules, and there is obvious charge transfer, indicating that it has high gas sensitivity to NO gas. In addition, the sensing performance of the gas sensor constructed by NO adsorption on upper, middle and lower layers of the P-BN2/P-G heterojunction is deeply studied. Transport calculations show that when NO is adsorbed on the upper and middle layers of the P-BN2/P-G heterojunction-based gas sensor, the current of the device decreases significantly. When adsorbed on the lower layer, the current shows a trend of first decreasing and then increasing. Under a bias of 0.1 V, the gas sensitivity can reach up to 49% when NO is adsorbed in the middle layer, which is substantially higher than that of the P-BN2 monolayer device. It can be seen that the gas sensitivity is significantly improved after forming the heterojunction. In addition, the bias transport spectrum and scattering state can reveal the change in device current caused by the adsorption of NO gas molecules, thereby clarifying its microscopic mechanism. Finally, all the findings indicate that penta-based materials can be used as a very promising gas-sensitive material for detecting NO.

Coupling effect of gas solubility in a solvent and substrate structure on performance in nanobubble morphological changes

The distribution morphologies of nanobubbles on Highly Oriented Pyrolytic Graphite (HOPG) surfaces prepared using the alcohol-water exchange test method were observed using atomic force microscopy. In situ observation revealed the distinct growth evolution behavior of nanobubble morphology. Molecular dynamics simulation was employed to replicate the experimental test and investigate the influence of the coupling effect of gas solubility and substrate structure on the morphological features of nanobubble distribution in alcohol-water exchange experiments. The results demonstrate that gas solubility plays a pivotal role in the nucleation of surface nanobubbles during alcohol-water exchange. Specifically, stable surface nanobubbles form only when the solubility exceeds 0.02535. Furthermore, under conditions where gas solubility satisfies the nucleation criteria, the surface potential energy of concave and defective structures exhibits concave characteristics, giving rise to the nucleation of cap-shaped nanobubbles. In contrast, the step structure, characterized by the smallest average surface potential energy, results in relatively flat properties in the lowest area, with nanobubble nucleation taking the form of layer-shaped features. yields relatively uniform characteristics at the lowest level, where nanobubble nucleation manifests in the form of layered features. As time progresses, cap-shaped nanobubbles coalesce, leading to the escape of gas molecules and subsequent dissipation, whereas the layer-shaped nanobubbles adsorb gas molecules from the solution, prompting their expansion.

Strain induced nitrobenzene sensing performance of MoSi2N4 monolayer: Investigation from density functional theory

The observing of environmental contaminant of Nitrobenzene (NB), from effluent discharges is a critical component of the surveillance to be conducted by public authorities and private sectors. By the way, the present work examines the NB adsorption behaviour of recently synthesized two-dimensional (2D) material MoSi2N4 through density functional theory (DFT). We observed that when increasing the percentage of strain (2, 4, 6 and 10 %) the adsorption energy also increasing reasonably compared to the unstrained case. The bandgap reduction was observed when gas molecule interacts with the strained MoSi2N4 and also the Bader charge calculation claims that the quantity of charge transferred between orbitals of N 2p of MoSi2N4 and the O 2p of NB. 4 % strain shows reasonable binding energy of 1.0201 eV with recovery time of 3.15 min. Moreover, there is strong bonding between N of MoSi2N4 and O of NB as evidenced from wavefunction analysis. 10 % strained system is stable at 600 K, which is examined through ab initio molecular dynamics study. The present theoretical investigation validates the 4 % strained MoSi2N4 can be fabricated as a sensor to detect the NB gas molecule.

Strong Metal–Support Interaction Induces Dual Reaction Sites for Ultrasensitive and Stable NO2 Detection in Extreme Environments

AbstractThe tripartite combination of a high density and stability of surface reaction sites, complemented by the longevity and efficient transfer of interface carriers, along with the effective adsorption and activation of target gas molecules, jointly determines the efficiency of chemiresistors. In this work, the strong metal–support interaction (SMSI) of Pt─Ce3+ is formed by the NaBH4 reduction method and thus prepares metal‐dynamically stable PtNR─CeO2 with Pt─Ce3+ and Pt─Pt reaction sites. The formation of SMSI induces the recombination of the chemical structure of the CeO2 surface causing the localization of electron‐rich Ce3+, which greatly increases the charge concentration at the interface. The experimental findings of the strong interaction of Pt─Ce3+ bonding and the catalytic effect of Pt optimized the adsorption mode of PtNR─CeO2 on target gas, which maintains stable catalytic activity at 20–500 °C and achieving a notable detection response value of 1.43 for 20 ppb NO2. This work offers fresh insights into designing stable oxide chemiresistors with efficiency and stability by customizing reaction sites at the atomic level.

Luminescence Changeable CO2-Storage Cylinder: Triple-Stranded Helical Eu(III)/Tb(III) Fluorinated MOFs with Amide Linkers.

Triple-stranded helical lanthanide MOFs with CO2 adsorption properties were investigated. Lanthanide MOFs ([Eu0.1Tb0.9(hfa)3(dpa)]n) are composed of lanthanide luminophores (Eu(III) and/or Tb(III) ions), fluorinated antenna ligands (hfa: hexafluoroacetylacetonate), and polyamide-type linker ligands (dpa: 4-(diphenylphosphoryl)-N-(4-(diphenylphosphoryl)phenyl)benzamide). The cylindrical structure was characterized by single-crystal X-ray analysis, thermogravimetric analysis, and gas adsorption measurements. The inner surfaces of the cylindrical channels were covered with the fluorine atoms of the hfa ligands. The emission intensity ratio (IEu/ITb) in [Eu0.1Tb0.9(hfa)3(dpa)]n is affected by the CO2 gas adsorption behavior. The change in IEu/ITb value was caused by the intermolecular interactions between the CO2 gas molecules and the fluorinated ligands, resulting in an electronic structural change of the lowest triplet excited state in the photosensitized hfa ligands.

The gas-sensing mechanism of Nb2C monolayer for SF6 decomposition based on the DFT study

Abstract In addressing malfunctions in gas-insulated switchgear (GIS) systems, it is imperative to have a real-time tracking system for SF6 decomposition products to guarantee the safety and reliability of the equipment's operation. Although a variety of gas detection technologies are currently available on the market, low-power gas detection devices for SF6 decomposition products are still in the development stage, and technological advances in this area are of great significance for improving the reliability of GIS systems. Based on the density functional theory (DFT), the Nb2C crystal surface structure was established and six adsorption structures of SO2, H2S, SOF2, SO2F2, HF and CO gas molecules on Nb2C crystal surface were constructed by geometrical optimization in this paper. The gas-sensitive properties of each adsorption system were explored in terms of adsorption energy, charge transfer, electron density, density of states and recovery time. The results showed that the Nb2C crystal surface was unfit HF and CO gases detection, both of which showed weak physical adsorption; the adsorption energies of SO2, H2S, SOF2, and SO2F2 on the Nb2C crystal surface were -1.846 eV, -1.081 eV, -5.270 eV, and -10.582 eV, respectively, and all of them were strong chemical adsorption. It was further shown by theoretical recovery time calculations that the Nb2C crystal surface can act as SOF2 and SO2F2 gas scavengers, and are able to desorb H2S (4.69 s) and SO2 (2.26 s) gases by appropriately increasing the temperature, but the Nb2C crystal surface is more suitable for use as a low-power gas-sensitive material for H2S gas detection. Therefore, Nb2C is anticipated to be a promising material for high response, low-power consumption and fast recovery for H2S gas detection in SF6 decomposition gas.

Experimental study on the dynamic threshold pressure gradient of high water-bearing tight sandstone gas reservoir

Tight sandstone water-bearing gas reservoirs typically exhibit low porosity and low permeability, with reservoir rocks characterized by complex pore structures, often featuring micron-scale or smaller pore throats. This intricate reservoir structure significantly restricts fluid flow within the reservoir, necessitating a certain threshold pressure gradient (TPG) to be overcome before flow can commence. This study focuses on the Ordos Basin and explores the influence of high water content tight sandstone gas reservoirs on TPG under different water saturation and formation pressure conditions through experiments. A mathematical model of TPG is established using multiple linear regression method. The results show that TPG is primarily affected by water saturation, followed by formation pressure. As the water saturation increases, the TPG of the core decreases, and the change becomes more pronounced when the water saturation exceeds 50%. As formation pressure increases, the weakening of the slippage effect in gas molecules leads to TPG stabilization, especially when local pressure exceeds 25.0 MPa. The research also shows that low-permeability cores exhibit greater TPG variation with pressure changes, while high-permeability cores remain more stable. A mathematical model was developed and validated to predict TPG based on permeability, water saturation, and formation pressure. These findings highlight the need to monitor formation water content during tight sandstone gas reservoir development to optimize production strategies, providing valuable insights for improving reservoir management and guiding future research.

A novel application of inverse gas chromatography for estimating contact angles in porous media

HypothesisSurface wettability is a critical factor in multi-phase flow within porous media, a processes essential in various applications e.g. in the energy sector. Traditional methods for assessing wettability of porous media by contact angle measurements, such as sessile droplet and micro-CT techniques, are limited by interface pinning, sample size or resolution impacting precision and accuracy. We hypothesized that using smaller and unconstrained probes, specifically gas molecules, to retrieve interactions along a representative sample size via inverse gas chromatography (IGC) could provide a more accurate determination of contact angles. MethodWe propose a procedure to relate IGC results with macro-scale wettability descriptions, such as the Young equation. To test the effectiveness of IGC method, glass bead samples with varying wettability, modified through a silanization process, were prepared. Contact angles for a distilled water-air-sample system were measured using the sessile droplet method and micro-CT for comparative analysis. IGC was employed to determine the surface energy components of these samples, which were then used in the extended Young-Dupré equation to calculate the contact angles. FindingsThe contact angle ranges determined by IGC and micro-CT for untreated glass beads, the most hydrophilic samples, showed great alignment. This consistency is attributed to the chemical amorphous nature of the untreated beads reflected in the assumption that dispersive and specific energetic components of surface sites are uncorrelated, on which the proposed analysis is based. For treated samples, where the silanization process creates correlations between surface energetic components, the alignment between IGC and micro-CT results was less precise. This study successfully demonstrated that IGC, a molecular-scale probe-based technique, can effectively determine the contact angle range, a macroscopic property, for amorphous samples. Future work should incorporate correlations between energetic components of surface detected by IGC to extend this method's applicability to a wider material range.

Selective passivation of 2D MoS2 nanosheets surface defects by spontaneous growth of Au nanoparticles for full response-recovery NO2 detection at room temperature

Full recovery at room temperature (RT) is quite challengng for two dimensional transition metal dichalcogenides chemiresistive gas sensors. The main reason for the incomplete recovery is the strong bonding of gas molecules onto sensing layer defects. Here, we show that the recovery rate of MoS2 chemiresistive NO2 sensors can be improved by selective passivation of MoS2 nanosheets (NSs) defects with Au nanoparticles (NPs) via a simple spontaneous reduction method. MoS2 NSs were produced by liquid shear exfoliation. Pristine and Au NPs functionalized MoS2 were characterized using ς-potential, UV–Visible spectroscopy, TEM, SEM, AFM, EDS, XRD, XPS and Raman spectroscopy. The analyses confirm the presence of Au NPs on the edges of MoS2 NSs at defective sites with NP sizes of 1–4 nm and 5–30 nm. Both pristine MoS2 and Au-decorated MoS2 NSs were employed to fabricate NO2 chemiresistive devices. Au-decorated MoS2 sensors showed an improved performance (for 1 ppm NO2, Au-MoS2 sensor exhibited a response of 5.6 % instead of 2.2 % for MoS2 sensor), and gave faster response and better recovery time. Concurrently, the functionalization is independent of the adsorption and desorption of NO2. Most importantly, the functionalization of MoS2 NSs helps to full response-recovery within one hour, without either thermal or UV irradiation treatment.

Carbon‐ and Nitrogen‐Based Complexes as Photocatalysts for Prebiotic and Oxygen Chemistry during Earth Evolution

AbstractSunlight has long served as primary energy source on our planet, shaping the behavior of living organisms. Extensive research has been dedicated to unraveling the evolutionary pathways involved. When the formation of Earth atmosphere, it primarily consisted of small gas molecules, which are considered crucial for the emergence of life. Recent demonstrations have shown that these molecules can also be transformed into semiconductors, with the potential to harness solar energy and catalyze chemical reactions as photocatalysts. Building upon this research, this minireview focuses on the potential revolutionary impact of photocatalysis on Earth. Initially, it examines key reactions, such as the formation of prebiotic molecules and the oxygen evolution reaction via water oxidation. Additionally, various C−N complexes in photocatalysts are explored, showcasing their roles in catalyzing chemical reactions. The conclusion and outlook provide a potential pathway for the evolution of Earth, shedding light on the significance of metal‐free photocatalysts in development of Earth.

Diffusion of N2/CH4/CO2 in Heptane-Containing Nanoblind Ends

The prevalence of micropores and nanopores in low-permeability reservoirs is a cause for concern, as it results in a sizeable quantity of oil reserves being trapped within them. The water-gas dispersion system has the capacity to expand the reservoirs’ wave volume and enhance oil recovery. While the microscopic oil repulsion mechanism has been the center of attention, the oil repulsion effect of three distinct types of gases (N2, CH4, and CO2) is of particular importance in understanding the displacement mechanism of N2/CH4/CO2 on heptane at the blind end of the nanometer. A molecular dynamics simulation using the LAMMPS software was employed to construct a model of a blind end of heptane on a SiO2 wall and an interface model with different types of gas molecules. This was done to investigate the microscopic mechanism of heptane replacement by gas molecules. The temperature (50 °C) and pressure (30 MPa) of the reservoir in the Changqing oil field are selected as the parameters for analysis. The findings indicate that all three types of gas molecules can enter the blind end and displace heptane. However, supercritical CO2 forms a mixed phase with heptane, which is more prone to extruding oil molecules situated near the inner wall surface of the blind end and desorbing the oil film. The results demonstrate that, in the context of the blind end, gaseous CO2 exhibits a lower solvation ability but superior extrusion diffusion ability for heptane compared to N2 and CH4. Furthermore, the interaction energy indicates that the interactions between two states of CO2 and heptane, as well as the thickness of the interface, increase with increasing pressure and temperature. The findings of this study elucidate the microscopic mechanism underlying the replacement of oil droplets or oil films at the blind end by different gases under reservoir conditions at the molecular level and offer further guidance for the selection of the gas phase and the replacement state in the water-gas dispersive drive system.

Adsorption and sensing performances of transition metal doped ZnO monolayer for CO and NO: A DFT study

In this study, theoretically, density functional theory was employed to explore the adsorption behavior of CO and NO prevalent hazardouss gases, on transition metal (TM = Fe, Co, Ni, and Cu) doped ZnO monolayer. The multifaceted analysis encompasses an array of critical aspects, including the adsorption structure, adsorption energy, density of states (DOS) and electron transfer to unravel the adsorption behavior. Our calculations show that TM atom doped ZnO monolayer exhibit high stability. TM doped can significantly enhance the interaction between the gas molecules (CO and NO) and the ZnO monolayer. Analysis of the recovery time and electrical conductivity of the adsorbed systems suggests that the Co-ZnO could be a suitable material for CO sensing,while the Cu-ZnO and Ni-ZnO can be used for NO sensing. These results suggest that transition metal doped can be a promising sensor candidate for toxic gas molecules adsorption and detection.

AlN Nanotube Decorated with Small Tin Oxide Clusters as a Novel CH4 Sensing Material.

The success of carbon nanotubes has triggered a great deal of research interest in other one-dimensional nanomaterials with the aim of designing innovative nanostructures with attractive and distinctive attributes for applications in sensing gas molecules and toxic substances. In the present study, first-principles density functional theory calculations were exploited to assess the capability of the small tin oxide cluster (SnxOy)-decorated (6,0)aluminum nitride (AlN) nanotube for detecting methane(CH4) in terms of energetic, structural, and electronic properties. We found that SnxOy clusters were chemisorbed on the surface of the AlN nanotube due to the considerable adsorption energy and the notable charge transfer from the former to the latter. Further calculations demonstrate that the energy band gap and work function of the AlN nanotube were reduced in the presence of additives. Benefiting from the higher affinity of SnxOy toward the CH4 molecule, the Sn3O3-decorated AlN nanotube exhibited the greatest CH4 adsorption energy. The electrical conductivity increased as the energy band gap and effective mass decreased dramatically. Additionally, the type of Sn3O3-decorated AlN nanotube changed from a p-type semiconductor to an n-type one after adsorbing the CH4 molecule. Therefore, the Sn3O3-decorated AlN nanotube endows great promise as a thermopower-based, resistance-based, and Seebeck-effect-based CH4 sensing material.

Understanding the Enhanced Separation Mechanism of C2H4/C2H6 at Low Pressure by HKUST−1

The production of ethylene (C2H4) is typically accompanied by the formation of impurities like ethane (C2H6), making the separation of C2H4 and C2H6 crucial in industrial processes. Here, we investigated the S-shaped adsorption phenomenon of C2H6 on the metal–organic framework HKUST−1. The virial equation is used to fit the C2H6 and C2H4 adsorption isotherms under low coverage. The results showed that the repulsion energy between neighboring C2H6 molecules was significantly higher than that between neighboring C2H4 molecules, which was an important reason for the lower adsorption of C2H6 by HKUST−1 at low coverage. As more molecules are adsorbed, gas molecules aggregate within pores, leading to more hydrogen bonds formed between HKUST−1 and larger-sized C2H6 under high coverage conditions. This phenomenon plays a crucial role in the S-shaped adsorption behavior of HKUST−1 on C2H6. Additionally, this unique adsorption behavior allows for the efficient separation of C2H4/C2H6 mixtures at low pressures. The ideal adsorbed solution theory (IAST) selectivity of HKUST−1 for C2H4/C2H6 mixtures was 3.78 at 283 K and 1 bar, but increased significantly to 7.53 under low pressure. This unique mechanism provides a theoretical basis for the low-pressure separation of C2H4/C2H6 by HKUST−1 and establishes a solid foundation for future practical research applications.

Machine Learnable Language for the Chemical Space of Nanopores Enables Structure-Property Relationships in Nanoporous 2D Materials.

The synthesis of nanoporous two-dimensional (2D) materials has revolutionized fields such as membrane separations, DNA sequencing, and osmotic power harvesting. Nanopores in 2D materials significantly modulate their optoelectronic, magnetic, and barrier properties. However, the large number of possible nanopore isomers makes their study onerous, while the lack of machine-learnable representations stymies progress toward structure-property relationships. Here, we develop a language for nanopores in 2D materials, called STring Representation Of Nanopore Geometry (STRONG), that opens the field of 2D nanopore informatics. We show that STRONGs are naturally suited for machine learning via recurrent neural networks, predicting formation energies/times of arbitrary nanopores and transport barriers for CO2, N2, and O2 gas molecules, enabling structure-property relationships. The machine learning models enable the discovery of specific nanopore topologies to separate CO2/N2, O2/CO2, and O2/N2 gas mixtures with high selectivity ratios. We also enable the rapid enumeration of unique configurations of stable, functionalized nanopores in 2D materials via STRONGs, allowing systematic searching of the vast chemical space of nanopores. Using the STRONGs approach, we find that a mix of hydrogen and quinone functionalization results in the most stable functionalized nanopore configuration in graphene, a discovery made feasible by expedited chemical space exploration. Additionally, we also unravel the STRONGs approach as ∼1000 times faster than graph theory algorithms to distinguish nanopore shapes. These advances in the language-based representation of 2D nanopores will accelerate the tailored design of nanoporous materials.