CO Molecules Research Articles

Unveiling the potential of aluminum-decorated 3D phosphorus graphdiyne as a catalyst for N2O reduction.

Interest in single-atom catalysts (SACs) has surged due to their potential to mitigate greenhouse N2O gas from the environment. In this study, we explore the potential of N2O reduction using porous 3D phosphorus graphdiyne decorated with an Al atom (3D-Al/PGDYN) through density functional theory. Results confirm the energetic stability of Al decorations on 3D-PGDYN and indicate that the Al atom plays an active role in catalysis. The N2O molecule undergoes spontaneous dissociation on the surface of the 3D-Al/PGDYN, initiating from the O-end, with a dissociation energy of -2.93 eV. In parallel, N2O dissociation through the N-end involves chemisorption onto the 3D-Al/PGDYN surface, with an adsorption energy (Ead) of -1.74 eV. The negative Ead values (-2.47 and -2.64 eV) indicate that CO and O2 species chemisorb onto the 3D-Al/PGDYN surface, but these energies are lower than that of N2O, suggesting that CO and O2 molecules do not hinder the N2O reduction process. Furthermore, the reaction CO + O* → CO2, which is vital for catalyst regeneration, proceeds swiftly on the 3D-Al/PGDYN catalyst with a low energy barrier of 0.11 eV, highlighting the catalyst's exceptional reactivity. This work holds significance in the design of catalysts and could be instrumental in developing new and efficient solutions for effectively removing harmful N2O from the environment.

A Supramolecular-Nanocage-Based Framework Stabilized by π-π Stacking Interactions with Enhanced Photocatalysis.

π frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π-π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular-nanocage-based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π-π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π-2). π-2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π-2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co-catalyst, the hydrogen evolution rate reaches a record-high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π-2 to the highly active Pt upon illumination. π-2 represents the unique stable supramolecular-cage-based π framework with excellent photocatalytic activity.

In Situ Exsolved CuZn Alloy Electrocatalysts for CO2 Conversion to Tunable Syngas Production

AbstractAlloying is considered as a promising method for syngas (H2 and CO mixture gas) generation. However, it is challenging to elucidate the relationship between the ratios of syngas and alloy components for CO2 reduction reaction. Herein, through tuning the Cu/Zn ratio on CuZn alloy, the H2/CO ratios in CuZn‐2 (Cu/Zn = 0.77) can be tuned in a noticeable range between 0.8 and 5.8 at −0.88 to −1.28 V versus RHE, and a durable stability of 12 h. The CuZn‐2 displays better performance and enhanced dynamics than other samples. Electrochemical impedance spectroscopies and Tafel results reveal that CuZn‐2 behaves kinetically optimized performance. Density functional theory calculations results reveal that CuZn alloy exhibits middle desorption intensity of *H for HER compared with pure Zn and Cu. CuZn alloy effectively decreases the energy barrier of CO2 molecules activated to *COOH relative to Zn, and also the alloy renders it easier for *CO desorb to generate CO for Cu. In situ Fourier transform infrared spectroscopies also observe a significant intensity of *CO on CuZn‐2. This work demonstrates that alloying Cu and Zn can create active sites, in which Cu acts as an auxiliary active site further facilitating *CO generation.

CO2 Reduction by Transition‐Metal Complex Systems: Effect of Hydrogen Bonding on the Second Coordination Sphere

AbstractHomogeneous electrocatalysts typified by transition‐metal complex show transcendent potency in efficient energy catalysis through molecular design. For example, metal complexes with elaborate design performed wonderful activity and selectivity for electrocatalytic CO2 reduction. Primary coordination sphere of metal complexes plays a key role in regulating its intrinsic redox properties and catalytic activity. However, the overall reduction efficiency of CO2 is also bound up with the substrate activation process. Transition‐metal complexes are hoped to exhibit reasonable redox potential, reactive activity, and stability, while binding and activating CO2 molecules to achieve efficient CO2 reduction. Construction of second coordination sphere, especially hydrogen‐bonding network of transition‐metal complexes, is reported to be the “kill two birds with one stone” strategy to realize efficient CO2 reduction catalysis via systematic catalyst properties modulation and substrate activation. Herein, we present recent progress on the construction of hydrogen‐bonding network in the second coordination sphere of metal complexes by ligand modification or the introduction of exogenous organic ligand, and the resulted productive enhancement of the catalytic performance of metal complexes by the improvement of adsorption capacity and activation of CO2, proton transfer rate, and stability of reaction intermediates, and so forth.

High-pressure supercritical CO2-assisted fabrication of two-dimensional LaAlO3 and its room temperature ferromagnetism

Abstract Spintronics applications in two-dimensional (2D) magnetic materials can significantly contribute to the miniaturization and energy efficiency of semiconductor devices. However, current 2D ferromagnetic materials face challenges such as ferromagnetic instability and low Curie temperature (Tc), which limit their broader application. In this study, 2D room-temperature ferromagnetic LaAlO3 was successfully prepared with supercritical carbon dioxide (SC CO2). With the enhanced stress effect of CO2 molecules, the contents of oxygen vacancies OV, aluminium vacancies AlV, and AlO4 in the 2D structure are elevated, and then the ferromagnetic properties of LaAlO3 appeared to be significantly enhanced due to defects and spatial symmetry breaking of the octahedron. Notably, the 2D intrinsic ferromagnetic LaAlO3 exhibited a Tc above 350 K. Therefore, this work supplies a new means for SC CO2 to modulate the microstructure and ferromagnetic properties of 2D LaAlO3, which is conducive to expanding the applications of LaAlO3.

Engineering Single Ni Sites on 3D Cage‐like Cucurbit[n]uril Ligands for Efficient and Selective CO2 Photocatalytic Reduction

Solar‐driven CO2 selective reduction with high conversion is a challenging task yet holds immense promise for both CO2 neutralization and green fuel production. Enhancing CO2 adsorption at the catalytic centre can trigger a highly efficient CO2 capture‐to‐conversion process. Herein, we introduce cucurbit[n]urils (CB[n]), a new family of molecular ligands, as a key component in the creation of a 3D cage‐like metal (nickel, Ni)‐complex molecular co‐catalyst (CB[7]‐Ni) for photocatalysis. It exhibits an unprecedented CO yield rate of 72.1 µmol· h‐1 with a high selectivity of 97.9% under visible light irradiation. To verify the origin of the carbon source in the products, a straightforward isotopic tracing method is designed based on tandem reactions. The catalytic process commences with photoelectron transfer from Ru(bpy)32+ to the Ni2+ site, resulting in the reduction of Ni2+ to Ni+. The locally enriched CO2 molecules in the cage ligand CB[7] undergo selective reduction by the Ni+ nearby to form CO product. This work exemplifies the inspiring potential of ligand structure engineering in advancing the development of efficient unanchored molecular co‐catalysts.

Engineering Single Ni Sites on 3D Cage-like Cucurbit[n]uril Ligands for Efficient and Selective CO2 Photocatalytic Reduction.

Solar-driven CO2 selective reduction with high conversion is a challenging task yet holds immense promise for both CO2 neutralization and green fuel production. Enhancing CO2 adsorption at the catalytic centre can trigger a highly efficient CO2 capture-to-conversion process. Herein, we introduce cucurbit[n]urils (CB[n]), a new family of molecular ligands, as a key component in the creation of a 3D cage-like metal (nickel, Ni)-complex molecular co-catalyst (CB[7]-Ni) for photocatalysis. It exhibits an unprecedented CO yield rate of 72.1 µmol· h-1 with a high selectivity of 97.9% under visible light irradiation. To verify the origin of the carbon source in the products, a straightforward isotopic tracing method is designed based on tandem reactions. The catalytic process commences with photoelectron transfer from Ru(bpy)32+ to the Ni2+ site, resulting in the reduction of Ni2+ to Ni+. The locally enriched CO2 molecules in the cage ligand CB[7] undergo selective reduction by the Ni+ nearby to form CO product. This work exemplifies the inspiring potential of ligand structure engineering in advancing the development of efficient unanchored molecular co-catalysts.

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.

Efficient CO2 Reduction Reaction on Cu-Decorated Biphenylene.

Developing efficient electrocatalysts for CO2 reduction into value-added products is crucial for a green economy. Inspired by the recent experimental synthesis of biphenylene (BPH) and the excellent catalytic activity of copper dispersed on two-dimensional (2D) materials, we chose to systematically investigate the pristine, defective, and Cu-decorated BPH for the electrocatalytic CO2 reduction to value-added hydrocarbons. It is observed that the CO2 molecules bind weakly to the pristine BPH, indicating their chemical inertness. Carbon single-vacancy defects facilitate CO2 adsorption with a strong binding energy (Eb) of -3.23 eV, detrimental to the CO2 reduction reaction (CRR) mechanism. We have further investigated the binding energy and kinetic stability of Cu-decorated BPH as a single-atom-catalyst (SAC). The molecular dynamics simulations confirm the kinetic stability, revealing that the Cu-atom avoids agglomeration under low metal dispersal conditions. The CO2 molecule gets adsorbed horizontally on the Cu-BPH surface with a ΔEb of -0.52 eV. The CRR mechanism is investigated using two pathways beginning with two different initial states, formate (*OCOH) and carboxylic (*COOH). The formate pathway confirms the conversion of *OCOH to *HCOOH with the rate-limiting potential (UL) of 0.39 eV for the production of HCOOH, while for the carboxylic pathway, the conversion of *COH to *CHOH has a UL of 0.32 eV, eventually producing CH3OH. Our findings highlight the role of Cu-BPH as an efficient SAC for CO2 catalytic activity to C1 products, as compared to the state-of-the-art Cu, and holds promise as an electrocatalyst for CRR.

Kinetics and Mechanism Study of Different Types of Surface‐Imprinted Polymers for CO2 Adsorption

ABSTRACTThe increased level of CO2 in the atmosphere has led to global warming and climate change. To mitigate these problems, solid adsorbents have become attractive materials for capturing excess CO2 in the post‐combustion method. Molecularly imprinted polymer (MIP) can be applied to prepare highly selective adsorbents that could capture CO2 molecules. The MIP was prepared using the surface imprinted polymer technique in this preliminary work. Only two types of support materials were used (graphite and silica gel) to screen the best support material that could enhance the CO2 adsorption capacity of the resulting adsorbent, which was analyzed using a fixed‐bed column reactor. Graphite‐imprinted polymer (GMIP) was found to be a good potential for CO2 adsorption. The Avrami model best described the adsorption system, while the fixed‐bed curve data fit the Yoon–Nelson model well. The semi‐empirical method was used to assess the interaction mechanism of the molecularly imprinted polymer with CO2 during adsorption. This investigation involved testing four different ratios of the template complex to functional monomers. The ratio of 1:4 (CO2:Allylthiourea) demonstrated the highest binding energy, with a higher formation of hydrogen bonds. Film diffusion and intraparticle diffusion were the main rate‐limiting steps that played vital roles at different stages of CO2 adsorption. This preliminary work has enhanced the development of MIP for CO2 adsorption and showcased the integration of computational approaches in tailoring specific MIPs.

Bond Dissociation Energy of CO2 with Spectroscopic Accuracy Using State-to-State Resolved Threshold Fragment Yield Spectra.

In this study, we present a precise determination of the bond dissociation energy of CO2 using state-to-state resolved threshold fragment yield spectra at a photoexcitation wavelength of around 92 nm. Our findings show that the bond dissociation energy of CO2, CO2 → CO + O, is 43976.12(15) cm-1 or 526.0714(18) kJ/mol. Furthermore, by incorporating our previously measured bond dissociation energies for CO and O2, we determined the dissociation energy of CO2 into C + O2 and the CO2 atomization energy (CO2 → C + O + O) to be 92309.73(21) and 133578.92(18) cm-1 or 1104.2699(25) and 1597.9592(22) kJ/mol, respectively. Thus, the bond dissociation energies of CO2 for all channels now have uncertainties of 0.2 cm-1 or 0.002 kJ/mol. These results serve as reference points for the enthalpies of C atom and CO and CO2 molecules and provide benchmarks for high-level ab initio quantum chemistry calculations.

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 is shown 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.

Rape straw biochar-assisted preparation of flower-like BiOCl with enriched oxygen vacancies for efficient photocatalytic CO2 reduction and pollutants degradation

Utilizing photocatalytic technology to transform CO2 into high added value chemical products has represented an effective strategy for alleviating the climate problems that have arisen due to excessive CO2 emissions. As a typical bismuth-based photocatalyst, BiOCl has garnered widespread attention due to its unique layered structure and low toxicity. However, the low light utilization efficiency and the rapid recombination of e−/h+ pairs severely hinder the practical application of BiOCl. Introducing oxygen vacancies (OVs) into BiOCl has been demonstrated to be one of the effective strategies for enhancing the photocatalytic performance of BiOCl. However, introduction of OVs through a mild and cost-effective approach remains a significant challenge. In this work, we developed a strategy for introducing OVs on BiOCl, which indues the growth of BiOCl into flower-like spherical structures and introduction of abundant OVs through addition of rape straw biochar (RC) under hydrothermal conditions. The synergistic interaction of RC and OVs endows with BiOCl more active sites as well as higher photogenerated carriers (e−/h+) separation efficiency. When the mass ratio of RC to BiOCl is 0.5 % (RC-0.5), the sample demonstrates the best performance, conversion of CO2 to CO on the sample is 4.0 μmol g−1 h−1, which is 3.08 times higher than that on the reference BiOCl. Additionally, versatility of the photocatalysts was further evaluated through photocatalytic degradation of rhodamine B (RhB) and perfluorooctanoic acid (PFOA). The degradation rate constant of RhB and PFOA on the RC-0.5 sample is 0.0642 min−1 and 0.00566 min−1, respectively, which is 2.26 times and 0.43 times higher than that on the reference BiOCl. Total organic carbon (TOC) experiments demonstrate that RhB can be effectively mineralized into CO2, H2O and small molecules on the photocatalyst. The main reactive species involved in the photocatalytic degradation process were investigated through active free radical trapping experiments and electron paramagnetic resonance (EPR). This work provides a viable strategy for the development of high-performance BiOCl photocatalysts for environmental applications.

Cascade CO2 Insertion in Carbanion Ionic Liquids Driven by Structure Rearrangement.

The CO2 chemisorption in state-of-the-art sorbents based on oxide/hydroxide/amine moieties is driven by strong chemical bonding formation in the carbonate/bicarbonate/carbamate products, which in turn leads to high energy input in sorbent regeneration. In addition, the CO2 uptake capacity was limited by the active sites' utilization efficiency, with each active site incorporating one CO2 molecule or less. In this work, a new concept and generation of sorbent was developed to achieve cascade insertion of multiple CO2 molecules by leveraging structure rearrangement as the driving force, leading to in situ generation of extra CO2-binding sites and significantly reduced energy input for CO2 release. The designed ionic liquids (ILs) containing carbanions with conjugated and asymmetric structure, deprotonated (methylsulfonyl)acetonitrile ([MSA]) anion, allowed the cascade insertion of two CO2 molecules via consecutive C-C and O-C bond formations. The proton transfer and structure rearrangement of the carboxylic acid intermediates played critical roles in stabilizing the first integrated CO2 and generating extra electron-rich oxygen sites for the insertion of the second CO2. The structure variation and reaction pathway were confirmed by operando spectroscopy, magnetic resonance spectroscopy (NMR), mass spectroscopy, and computational chemistry. The energy input in sorbent regeneration could be further reduced by harnessing the phase-changing behavior of the carbanion salts in ether solutions upon reacting with CO2, avoiding the energy consumption in heating the solvent. The fundamental insights obtained herein provide a promising approach to greatly improve the CO2 sorption performance via sophisticated molecular-scale structural engineering of the sorbents.

Ignition of anthracite microparticles by continuous laser radiation with wavelengths of 450 and 808 nm

The energy and spectral-kinetic characteristics of ignition of anthracite microparticle powders with a bulk density of 0.5 g/cm3 were measured when exposed to continuous laser radiation at wavelengths λ = 450 and 808 nm with an exposure time of 1 second. Ignition delay times were measured depending on the radiation power density and critical values of the ignition energy density of anthracite samples were determined. The energy cost of igniting anthracite for radiation with λ = 450 nm is less than for radiation with λ = 808 nm. In the emission spectra of anthracite resulting from the absorption of laser radiation, there is a glow associated with the release and ignition of volatile substances (flame CO, glow of excited molecules CO, C2 and H2O) and thermal glow associated mainly with the heated surface of the samples, as well as the flight of incandescent carbon particles.

Dual-active-group co-modification of BiOBr for boosting photocatalytic CO2 reduction coupled with ciprofloxacin oxidation

Coupling CO2 photoreduction with ciprofloxacin (CIP) oxidation presents a promising strategy for achieving not only the complete utilization of photoexcited carriers but also the win–win goals of energy conversion and environmental remediation. In this study, we utilized an aminated BiOBr catalyst with surface hydroxyl groups (NH2/BOB–OH) for efficient photocatalytic CO2 reduction coupled with CIP oxidation. In this process, hydroxyl (OH) and amino groups (NH2) adsorbed and activated CIP (an organic pollutant) and CO2 molecules, respectively, promoting the overall photocatalytic redox activity. Remarkably, 0.5NH2/BOB–OH exhibited excellent photocatalytic redox performance for CO2 reduction coupled with CIP oxidation, with the CO yield and CIP degradation efficiency being 6.85 and 1.08 times higher, respectively, than those achieved using BiOBr without any active groups. Moreover, a series of in situ experimental characterizations and theoretical simulations revealed that these two opposing active groups not only accelerated carrier separation but also boosted the surface reactivity of the catalyst. These findings provide helpful insights into the dual-active-group functionalization of semiconductors, leading to their high photoredox activity for energy conversion along with environmental remediation.

A Survey of Reaction Energetics for Diverse Small Molecule Activation: Where Do Molecular Electrocatalysts Go From Here?

AbstractThe invention of technologies that can activate, transform, and upgrade small molecules is a significant challenge. The starting point for many such technologies is molecular catalysts. Their well‐defined active sites, multitude of tools to characterize their reactions, and their synthetic flexibility makes such molecules logical starting points. However, it is increasingly clear that challenges exist in the applications of molecular catalysts at the scales needed to address modern chemical and energy demands. In this review, we discuss selected classes of molecular electrocatalysts and highlight their development and key features. Of special interest are proton‐coupled transformations of H2, O2, N2, CO2, and related small molecules. We also frame important thermodynamic features for different catalysts using new approaches and ask forward looking questions about their applications in practical systems.

Abundant interfacial and intrinsic oxygen vacancies enabling small nickel/ceria nanocrystal efficient CO2 methanation

Smaller nano-sizes typically result in supported catalysts with abundant interfacial and intrinsic oxygen vacancies for better adsorption and activation of small molecules, including CO2, leading to improved efficiency of CO2 methanation. Here, Ni/CeO2-S with the smaller nano-size of around 4.2 nm is used to catalyze CO2 methanation, which exhibits significantly enhanced activity compared to larger nano-sized Ni/CeO2-L catalyst, even surpassing the most majority of previously reported catalysts using CeO2 as the support or Ni as the active metal. The coexistence of interfacial defects and intrinsic oxygen vacancies allows for enhanced adsorption and activation of CO2 molecules as well as H spillover, resulting in such improved CO2 methanation. In-situ DRIFTS demonstrate a nearly sole Formate pathway on Ni/CeO2-S for efficient CO2 hydrogenation. This research provides valuable insights into the reaction mechanism over a small nanosize supported catalyst.

Numerical simulation for subsidence control in CO2 storage and methane hydrate extraction

Gas hydrates are increasingly viewed as a promising alternative to traditional fossil fuels. However, their extraction process poses risks to structural integrity, potentially causing significant subsidence. In this study, we developed a Thermo-Hydro-Mechanical-Chemical (THMC) model to analyze the impact of gas hydrate extraction on seabed subsidence. Our investigation focused on the influence of bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity on subsidence during gas hydrate extraction via depressurization.The results show that seabed subsidence is affected by various factors such as bottom hole flowing pressure, initial hydrate concentration, gas saturation, permeability, porosity, and rock thermal conductivity. It was noted that significant subsidence is associated with low initial hydrate concentration, high permeability, porosity, low gas saturation, low rock thermal conductivity, and a notable pressure drop of 79.31%.To address this issue, we propose a seabed subsidence mitigation strategy involving CO2 injection. This approach not only safeguards offshore infrastructure and coastal communities but also helps reduce CO2 emissions, aligning with global climate change mitigation efforts. In our model, CO2 injection occurs in the subsurface reservoir at the interface between the free water zone and hydrate-bearing formations. The CO2 hydrates formation process releases heat, which dissociates methane hydrates, allowing the methane to be replaced by CO2 molecules and move towards the production well.Our analysis reveals that increasing injection temperature and rate significantly reduces subsidence. Additionally, the range of investigated injection pressures, which included pressures equal to and more than double the initial reservoir pressure, showed inconsequential impacts on seabed subsidence.The effectiveness of subsidence reduction is significantly enhanced by injecting a CO2/N2 mixture compared to pure CO2 injection. The most substantial reduction in subsidence occurred when a mixture of CO2 and N2 in a 50/50 vol/vol ratio was injected at a high rate.These findings offer crucial insights for optimizing the efficiency and control of gas hydrate extraction methods. They emphasize the importance of employing balanced injection strategies to minimize environmental risks and ensure sustainable energy extraction.

Molecular Insights into CO2 Diffusion Behavior in Crude Oil

CO2 flooding plays a significant part in enhancing oil recovery and is essential to achieving CCUS (Carbon Capture, Utilization, and Storage). This study aims to understand the fundamental theory of CO2 dissolving and diffusing into crude oil and how these processes vary under reasonable reservoir conditions. In this paper, we primarily use molecular dynamics simulation to construct a multi-component crude oil model with 17 hydrocarbons, which is on the basis of a component analysis of oil samples through laboratory experiments. Then, the CO2 dissolving capacity of the multi-component crude was quantitatively characterized and the impacts of external conditions—including temperature and pressure—on the motion of the CO2 dissolution and diffusion coefficients were systematically investigated. Finally, the swelling behavior of mixed CO2–crude oil was analyzed and the diffusion coefficients were predicted; furthermore, the levels of CO2 impacting the oil’s mobility were analyzed. Results showed that temperature stimulation intensified molecular thermal motion and increased the voids between the alkane molecules, promoting the rapid dissolution and diffusion of CO2. This caused the crude oil to swell and reduced its viscosity, further improving the mobility of the crude oil. As the pressure increased, the voids between the internal and external potential energy of the crude oil models became wider, facilitating the dissolution of CO2. However, when subjected to external compression, the CO2 molecules’ diffusing progress within the oil samples was significantly limited, even diverging to zero, which inhabited the improvement in oil mobility. This study provides some meaningful insights into the effect of CO2 on improving molecular-scale mobility, providing theoretical guidance for subsequent investigations into CO2–crude oil mixtures’ complicated and detailed behavior.