Quantum molecular dynamic simulations are introduced to study the dynamical, electrical, and optical properties of carbon dioxide under dynamic compressions. The principal Hugoniot derived from the calculated equation of states is demonstrated to be well accordant with experimental results. Molecular dissociation and recombination are investigated through pair correlation functions, and decomposition of carbon dioxide is found to be between 40 and 50 GPa along the Hugoniot, where nonmetal-metal transition is observed. In addition, the optical properties of shock compressed carbon dioxide are also theoretically predicted along the Hugoniot.
Team C2CNT, or team Carbon dioxide to carbon nanotubes, proprietary technology directly removes the widest range of carbon dioxide from the ecosystem. C2CNT technology simply transforms low to high carbon dioxide into carbon and oxygen, and the carbon produced is permanently removed, that is stable on the order of geologic time frames. C2CNT technology directly removes, transforms and stores atmospheric 0.04% CO2 without pre-concentration from the air, or 5% CO2 removal of gas power plant CO2 emissions, or 12.5% CO2 removal of coal power plant CO2 emissions, or 33% CO2 (pertinent to the comple…
In recent years, the scientific community has given more and more attention to the issue of climate change and global warming, which is largely attributed to the massive quantity of carbon dioxide emissions. Thus, the demand for a carbon dioxide capture material is massive and continuously increasing. In this study, we perform first-principle calculations based on density functional theory to investigate the carbon dioxide capture ability of pristine and doped beryllonitrene. Our results show that carbon dioxide had an adsorption energy of -0.046 eV on pristine beryllonitrene, so it appears th…
We have performed quantum chemical computational studies to determine carbon dioxide affinity to carbon compounds and minerals, which could be present in shales. These studies shed light on the microscopic mechanisms of the possible carbon oxide sequestration processes. Our studies reveal that the carbon oxide can be adsorbed to various forms of carbon structures and also minerals such as periclase or illite. We find out that the strongest affinity of carbon oxide towards carbon structures occurs when the carbon structures exhibit $sp^3$ bonds.
Within the field of nanotechnology, nano-scale composites have significant potential in the development of advanced materials for functional applications. Here, composites based on carbon nanotubes and titanium dioxides have been prepared with titanyl sulfate using a chemical bath deposition method at or near room temperature. Two kinds of titanium dioxide depositions corresponding to rutile and anatase were sheathed on carbon nanotubes evenly by adjusting the precursor concentration and temperature. Possible composite mechanisms are discussed. Compared with original tubes, the specific surfac…
We present a theoretical study of solid carbon dioxide up to 50GPa and 1500K using first-principles calculations. In this pressure-temperature range, interpretations of recent experiments have suggested the existence of CO2 phases which are intermediate between molecular and covalent-bonded solids. We reexamine the concept of intermediate phases in the CO2 phase diagram and propose instead molecular structures, which provide an excellent agreement with measurements.
Based on first principles density functional theory calculations we explore the energetics of the conversion of carbon mono and dioxide to methane over graphene oxide surfaces. Similar to the recently discovered hydration of various organic species over this catalyst, the transfer of hydrogen atoms from hydroxyl groups of graphene oxide provide a step by step transformation hydrogenation of carbon oxides. Estimated yields of modeled reactions at room temperature are about 0.01% for the carbon mono and dioxide. For the modeling of graphene oxide/metal oxide composites, calculations in the prese…
Carbon dioxide, CO2, capture by room-temperature ionic liquids (RTILs) is a vivid research area featuring both accomplishments and frustrations. This work employs the PM7-MD method to simulate adsorption of CO2 by 1,3-dimethylimidazolium thiocyanate at 300 K. The obtained result evidences that the thiocyanate anion plays a key role in gas capture, whereas the impact of the 1,3-dimethylimidazolium cation is mediocre. Decomposition of the computed wave function on the individual molecular orbitals confirms that CO2-SCN binding extends beyond just expected electrostatic interactions in the ion-mo…
The sheet samples of thermally exfoliated graphite (TEG) carbon nanotubes (CNT) composites (TEG CNT cs) were obtained by persulphate oxidation using chemical (CO) and electrochemical (anode) oxidation (ECAO). Electron microscopy reveals multi layered structures of few layer graphene nanosheets with folded and tubular like fragments.Electron microscopy reveals multilayered structures of few layer graphene nanosheets with folded and tubular like fragments. The effective thermal diffusivity values were estimated by nonstationary photo-pyroelectric thermophysical characterization using the heat pu…
Carbon dioxide fixation and storage constitute a drastically important problem for the humanity nowadays. We hereby publish a new solution based on the alkaline earth salts with a weakly coordinating anion, tetrakis(pentafluorophenyl)borate. The proposed solution was validated using a robust combination of global minimum search and molecular dynamics simulations utilizing a well-tested, reliable semiempirical Hamiltonian to monitor chemical reactions. Calcium tetrakis(pentafluorophenyl)borate captures 5.5 CO2 molecules per mole, whereas barium tetrakis(pentafluorophenyl)borate captures 3.6 CO2…
A climate mitigation comprehensive solution is presented through the first high yield, low energy synthesis of macroscopic length carbon nanotubes (CNT) wool from CO2 by molten carbonate electrolysis, suitable for weaving into carbon composites and textiles. Growing CO2 concentrations, the concurrent climate change and species extinction can be addressed if CO2 becomes a sought resource rather than a greenhouse pollutant. Inexpensive carbon composites formed from carbon wool as a lighter metal, textiles and cement replacement comprise a major market sink to compactly store transformed anthropo…
Large-scale applications are waiting for an optimal CO2 scavenger to reinforce CCS and CCU technologies. We herein introduce and succinctly validate a new philosophy of capturing gaseous CO2 by negatively-charged carbonaceous structures. The chemical absorption of CO2 turns out possible thanks to the emergence of significant nucleophilic interaction carbon centers upon applying voltage. The carbonaceous cathode, therefore, may serve as a prototype of a new CO2 sorbent. As a model to simulate chemisorption, we used a small-sized graphene quantum dot (GQD). According to the recorded reaction pro…
We report the atomic layer deposition of titanium dioxide on carbon nanosheet templates and investigate the effects of post-deposition annealing in a helium environment using different characterization techniques. The crystallization of the titanium dioxide coating upon annealing is observed using in-situ X-ray diffraction. The (micro)-structural characterization of the films is carried out by scanning electron microscopy and advanced transmission electron microscopy techniques. Our study shows that the annealing of the atomic layer deposition processed and carbon nanosheets templated titanium…
We study numerically the adsorption of a mixture of CO$_2$ and CH$_4$ on a graphite substrate covered by graphene nanoribbons (NRs). The NRs are flat and parallel to the graphite surface, at a variable distance ranging from 6 Å to 14 Å. We show that the NRs-graphite substrate acts as an effective filter for CO$_2$. Our study is based on Molecular Dynamics (MD) simulations. Methane is considered a spherical molecule, and carbon dioxide is represented as a linear rigid body. Graphite is modeled as a continuous material, while the NRs are approached atomistically. We observe that when the NRs are…
Development of new greenhouse gas scavengers is actively pursued nowadays. Volatility caused solvent consumption and significant regeneration costs associated with the aqueous amine solutions motivate search for more technologically and economically advanced solutions. We hereby used hybrid density functional theory to characterize thermodynamics, structure, electronic and solvation properties of amino and carboxamido functionalized C60 fullerene. C60 is non-volatile and supports a large density of amino groups on its surface. Attachment of polar groups to fullerene C60 adjusts its dipole mome…
Although numerous investigations reveal the gas physisorption characteristics of porous materials and a variety of theories have also established to describe gas physisorption during the past century, the essence of physisorption behavior of gas within nanoscale space is still indistinct. We find that the physisorption behavior of complex molecular system of methane and carbon dioxide within nanoporous materials exhibits a quantum effect. Based on this quantum effect, we established a physisorption equation from the perspective of quantum mechanics to re-understand the basic principles of gas …
Charge transfer between molecules and catalysts plays a critical role in determining the efficiency and yield of photo-chemical catalytic processes. In this paper, we study light-induced electron transfer between transition metal doped aluminium clusters and CO$_2$ molecules using first-principles time-dependent density-functional theory. Specifically, we carry out calculations for a range of dopants (Zr, Mn, Fe, Ru, Co, Ni and Cu) and find that the resulting systems fall into two categories: Cu- and Fe-doped clusters exhibit no ground state charge transfer, weak CO$_2$ adsorption and light-in…
The FAST Framework: Developing a Data-Efficient Machine Learning Potential to Decode Superionic Transition-Induced Thermophysical and Kinetic Anomalies in UO2 under Extreme Conditions
State Key Laboratory for Strength and Vibration of Mechanical Structures, Shaanxi Engineering Laboratory for Vibration Control of Aerospace Structures, School of Aerospace, Xi'an Jiaotong University（西安交通大学航天学院）；Aircraft Strength Research Institute of China（中国飞机强度研究所）
Methanation of carbon dioxide over ceria-praseodymia promoted Ni-alumina catalysts. Influence of metal loading, promoter composition and alumina modifier
Metal-organic framework (MOFs) are nanoporous materials that could be used to capture carbon dioxide from the exhaust gas of fossil fuel power plants to mitigate climate change. In this work, we design and train a message passing neural network (MPNN) to predict simulated CO$_2$ adsorption in MOFs. Towards providing insights into what substructures of the MOFs are important for the prediction, we introduce a soft attention mechanism into the readout function that quantifies the contributions of the node representations towards the graph representations. We investigate different mechanisms for …
Using quantum molecular dynamic simulations, we have studied the thermophysical properties of warm dense carbon monoxide under extreme conditions. The principal Hugoniot, which is derived from the equation of state, shows excellent agreement with available experimental data up to 67 GPa. The chemical decomposition of carbon monoxide has been predicted at 8 GPa by means of pair correlation function. Based on Kubo-Greenwood formula, the dc electrical conductivity and the optical reflectivity are determined, and the nonmetal-metal transition for shock compressed carbon monoxide is observed around…
The supercritical state is currently viewed as uniform and homogeneous on the pressure-temperature phase diagram in terms of physical properties. Here, we study structural properties of the supercritical carbon dioxide, and discover the existence of persistent medium-range order correlations which make supercritical carbon dioxide non-uniform and heterogeneous on an intermediate length scale, a result not hitherto anticipated. We report on the carbon dioxide heterogeneity shell structure where, in the first shell, both carbon and oxygen atoms experience gas-like type inter- actions with short …
Ubiquitous graphene is a stricly 2D material representing an ideal adsorbing platform due to its large specific surface area as well as its mechanical strength and resistance to both thermal and chemical stresses. However, graphene as a bulk material has the tendency to form irreversible agglomerates leading to 3D graphitic structures with a significant decrease of the area available for adsorption and no room for gas intercalation. In this paper a novel nanoporous graphite formed by graphtriyne sheets is introduced: its 3D structure is theoretically assessed by means of electronic structure a…
Nano-materials, such as metal-organic frameworks, have been considered to capture CO$_2$. However, their application has been limited largely because they exhibit poor selectivity for flue gases and low capture capacity under low pressures. We perform a high-throughput screening for selective CO$_2$ capture from flue gases by using first principles thermodynamics. We find that elements with empty d orbitals selectively attract CO$_2$ from gaseous mixtures under low CO$_2$ pressures at 300 K and release it at ~450 K. CO$_2$ binding to elements involves hybridization of the metal d orbitals with…
Supercapacitors capable of providing high voltage, energy and power density but yet light, low volume occupying, flexible and mechanically robust are highly interesting and demanded for portable applications. Herein, freestanding flexible hybrid electrodes based on MnO2 nanoparticles grown on macroscopic carbon nanotube fibers (CNTf-MnO2) were fabricated, without the need of any metallic current collector. The CNTf, a support with excellent electrical conductivity, mechanical stability, and appropriate pore structure, was homogeneously decorated with porous akhtenskite ε-MnO2 nanoparticles pro…
Imidazolium based porous cationic polymers were synthesized using an innovative and facile approach, which takes advantage of the Debus Radziszewski reaction to obtain meso- and microporous polymers following click chemistry principles. In the obtained set of materials, click based porous cationic polymers have the same cationic backbone, whereas they bear the commonly used anions of imidazolium poly(ionic liquid)s. These materials show hierarchical porosity and a good specific surface area. Furthermore, their chemical structure was extensively characterized using ATR FTIR and SS NMR spectrosc…
We have investigated the fractal characteristics and shape complexity of the fracture surfaces of swelled isotactic polypropylene Y1600 in supercritical carbon dioxide fluid through the consideration of the statistics of the islands in binary SEM images. The distributions of area $A$, perimeter $L$, and shape complexity $C$ follow power laws $p(A)\sim A^{-(μ_A+1)}$, $p(L)\sim L^{-(μ_L+1)}$, and $p(C)\sim C^{-(ν+1)}$, with the scaling ranges spanning over two decades. The perimeter and shape complexity scale respectively as $L\sim A^{D/2}$ and $C\sim A^q$ in two scaling regions delimited by $A\…
This study introduces the high yield, electrolytic synthesis of carbon nanofibers, CNFs, directly from carbon dioxide. Production of a precious commodity such as CNFs from atmospheric carbon dioxide provides impetus to limit this greenhouse gas and mitigate the rate of climate change. CNFs are formed at high rate using inexpensive nickel and steel electrodes in molten electrolytes. The process is demonstrated as a scaled-up stand-alone electrolytic cell, and is also shown compatible with the STEP, solar thermal electrochemical process, using concentrated sunlight at high solar to electric effi…
Global warming is seen as a drastic environmental problem nowadays. Carbon dioxide (CO 2 ) concentration in the Earth's atmosphere is linked to the average temperature on the surface of the planet. Carbon capture and storage is an important technological endeavor aiming to improve the ecology. The present work investigates reaction paths that are responsible for CO 2 chemisorption by the ammonium- and phosphonium-based ionic liquids containing an aprotic heterocyclic anion 2-cyanopyrrolidine. We show that two moles of CO 2 per one mole of the gas scavenger can be theoretically fixed by such io…
A novel system containing nanoporous materials and carbonate ions is proposed, which is capable to capture CO2 from ambient air simply by controlling the amount of water (humidity) in the system. The system absorbs CO2 from the air when the surrounding is dry, whereas desorbs CO2 when wet. A design of such a CO2 absorption/desorption system is investigated in this paper using molecular dynamics and quantum mechanics simulations, and also verified by experiments. Its working mechanism is revealed as the reduction of free energy of the carbonate ion hydrolysis with the decrease of the number of …
We have performed a thorough computational study to assess the accuracy of density functional theory (DFT) methods in describing the interactions of CO2 with model alkali-earth-metal (AEM, Ca and Li) decorated carbon structures, namely anthracene (C14H10) molecules. We find that gas-adsorption energy and equilibrium structure results obtained with both standard (i.e. LDA and GGA) and hybrid (i.e. PBE0 and B3LYP) exchange-correlation functionals of DFT differ significantly from results obtained with second-order Moller-Plesset perturbation theory (MP2), an accurate computational quantum chemist…
The formation and disassociation of excitons plays a crucial role in any photovoltaic or photocatalytic application. However, excitonic effects are seldom considered in materials discovery studies due to the monumental computational cost associated with the examination of these properties. Here, we study the excitonic properties of nearly 50 photocatalysts using state-of-the-art Bethe-Salpeter formalism. These $\sim$ 50 materials were recently recognized as promising photocatalysts for CO$_2$ reduction through a data-driven screening of 68,860 materials. Here, we propose three screening criter…
In order to separate a mixture of hydrogen ($H_2$) and carbon dioxide ($CO_2$) gases, we have proposed a new approach employing the graphdiyne-like membrane (GDY-H) using density functional theory (DFT) calculations and molecular dynamics (MD) simulations. GDY-H is constructed by removing one-third diacetylenic ($-$C$\equiv$C$-$C$\equiv$C$-$) bonds linkages and replacing with hydrogen atoms in graphdiyne structure. Our DFT calculations exhibit poor selectivity and good permeances for $H_2$/$CO_2$ gases passing through this membrane. To improve the performance of the GDY-H membrane for $H_2$/$C…
A number of simple pair interaction potentials of the carbon dioxide molecule are investigated and found to underestimate the magnitude of the second virial coefficient in the temperature interval 220 K to 448 K by up to 20%. Also the third virial coefficient is underestimated by these models. A rigid, polarizable, three-site interaction potential reproduces the experimental second and third virial coefficients to within a few percent. It is based on the modified Buckingham exp-6 potential, an anisotropic Axilrod-Teller correction and Gaussian charge densities on the atomic sites with an induc…
Ceria (CeO2) is a promising catalyst for the reduction of carbon dioxide (CO2) to liquid fuels and commodity chemicals, in part because of its high oxygen storage capacity, yet the fundamentals of CO2 adsorption and initial activation on CeO2 surfaces remain largely unknown. We use density functional theory, corrected for onsite Coulombic interactions (DFT+U), to explore various adsorption sites and configurations for CO2 on stoichiometric and reduced CeO2 (110). Our model of reduced CeO2 (110) contains oxygen vacancies at the topmost atomic layer and undergoes surface reconstruction upon intr…
We report results from grand-canonical Monte Carlo simulations of methane and carbon dioxide adsorption in structure sI gas hydrates. Simulations of pure component systems show that all methane sites are equivalent, while carbon dioxide distinguishes between two types of sites, large or small. The adsorbed mixture can be regarded as ideal, as long as only large sites are occupied. A strong preference is demonstrated for methane, when the smaller sites become filled. The molar heat of adsorption of methane decreases with composition, while the molar heat of adsorption for carbon dioxide passes …
With a view towards optimizing gas storage and separation in crystalline and disordered nanoporous carbon-based materials, we use ab initio density functional theory calculations to explore the effect of chemical functionalization on gas binding to exposed edges within model carbon nanostructures. We test the geometry, energetics, and charge distribution of in-plane and out-of-plane binding of CO2 and CH4 to model zigzag graphene nanoribbons edge-functionalized with COOH, OH, NH2, H2PO3, NO2, and CH3. Although different choices for the exchange-correlation functional lead to a spread of values…
The phase stability and equilibria of carbon dioxide is investigated from 125 -- 325K and 1 -- 10,000 atm using extensive molecular dynamics (MD) simulations and the Two-Phase Thermodynamics (2PT) method. We devise a direct approach for calculating phase diagrams in general, by considering the separate chemical potentials of the isolated phase at specific points on the P-T diagram. The unique ability of 2PT to accurately and efficiently approximate the entropy and Gibbs energy of liquids thus allows for assignment of phase boundaries from relatively short ($\mathrm{\sim}$ 100ps) MD simulations…
