Andrey V. Shkolin

The present work focuses on the results of the study of adsorption of carbon dioxide and nitrogen onto the synthesized metal-organic framework polymer (MOF) ZrBDC-NH₂. The isotherms were recorded at temperatures of 243, 273, 293, and 333 K within the pressure range of 0 to 120 kPa. The isotherms of individual gas adsorption were calculated using the Dubinin–Radushkevich (D–R) equation within the framework of the theory of volume filling of micropores (TVFM). The IAST method was used to predict the adsorption of the binary CO₂/N₂ mixture with the gas component ratio of 0.04/99.96 vol %. The differential molar isosteric heat of CO₂ adsorption and the separation coefficients were evaluated. The applicability of ZrBDC-NH₂ MOF for the direct adsorption removal of carbon dioxide from the air was assessed.

Thermal effects of adsorption and desorption, leading to temperature fluctuations and losses of adsorption storage systems capacity in the processes of gas charging and discharging, are the main obstacle to the wide practical application of adsorbed natural gas (ANG) technology. This work presents a numerical simulation of heat and mass transfer processes under various cyclic operation modes of a full-scale adsorption storage tank with various thermal control systems. The high-density monolithic adsorbent KS-HAM, obtained on the basis of industrial activated carbon KS-HA, was used as the adsorption material. The phase composition, surface morphology, and porous structure of the sorbents were studied. The adsorption of methane on the KS-HA adsorbent was measured. It is shown that increasing the duration of charging leads to obtaining additional capacity of the ANG system; however, the final efficiency and benefit at the end of the charging–discharging cycle are determined by the efficiency of the thermal control system and the gas-discharging mode. It has been shown that the presence of a finned thermal control system allows for charging the adsorption storage tank 3–8 times faster and provides an 8–24% greater amount of gas discharged at the discharging stage compared to the ANG system without fins.

Стресс-эффект адсорбционной деформации углеродного адсорбента на основе каменноугольного сырья при адсорбции метана Стресс-эффект адсорбционной деформации углеродного адсорбента на основе каменноугольного сырья при адсорбции метана

Equilibrium and kinetic behavior of adsorption-induced deformation have attracted a lot of attention in the last few decades. The theoretical and experimental works cover activated carbons, coals, zeolites, glasses, etc. However, most of the theoretical works describe only the equilibrium part of the deformation process or focus on the time evolution of the adsorption process. The present paper aims to cover the existing gap using the thermodynamic framework combined with the diffusion-based description of adsorbate time evolution inside an adsorbent. We obtained self-consistent equations describing equilibrium and out-of-equilibrium adsorption, as well as deformation processes. Further, the obtained equations were verified on the experimental data of carbon dioxide and methane on activated carbons. The model is capable of describing both equilibrium and kinetic adsorption and adsorption-induced deformation data. Additionally, we studied the possible influence of slow relaxation processes in the adsorbent on the adsorption process. The current work helps to interpret experimental data for time-dependent adsorption-induced deformation.

One-stage synthesis technology for preparing carbon adsorbents with tailored porosity from agricultural waste is worthwhile due to their extensive application value. Thermal gravimetric analysis, low-temperature N₂ adsorption, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and Raman spectroscopy were used to record the structure transformations of carbon materials, namely pore development, proceeding in the course of the step-wise pyrolysis of renewable and low-cost raw materials such as walnut shells (WNSs), which was carried out within a temperature range of 240–950 °C in a CO₂ flow. The minimum threshold carbonization temperature for preparing nanoporous carbon materials from WNSs, determined by the examination of the N₂ adsorption data, was 500 °C. The maximum specific micropore volume and BET surface achieved in the process without holding a material at a specified temperature were only 0.19 cm³/g and 440 m²/g, respectively. The pyrolysis at 400–600 °C produced amorphous sp² carbon. At a temperature as high as 750 °C, an increase in the X-ray reflection intensity indicated the ordering of graphite-like crystallites. At high burn-off degrees, the size of coherently scattering domains becomes smaller, and an increased background in X-ray patterns indicates the destruction of cellulose nanofibrils, the disordering of graphene stacks, and an increase in the amount of disordered carbon. At this stage, pores develop in the crystallites. They are tentatively assigned to crystallites with sizes of 15–20 nm and to micropores. According to the Raman spectra combined with the XRD and SAXS data, the structure of all the pyrolysis products is influenced by the complex structure of the walnut shell precursor, which comprises cellulose nanofibrils embedded in lignin. This structure was preserved in the initial stage of pyrolysis, and the graphitization of cellulose fibrils and lignin proceeds at different rates. Most of the pores accessible for gas molecules in the resulting carbon materials are associated with former cellulose fibrils.

The results of experimental studies of the deformation of a microporous carbon adsorbent based on АР-В coal raw material during the adsorption of methane in the region of supercritical temperatures at pressures up to 10 MPa are presented. It is shown that in the initial filling region, the adsorbent experiences a deformation stress effect that depends on temperature. A model is proposed to explain the observed deformation effects.

A noncovalent integration of nanosheets of molybdenum disulfide (MoS₂) and the zinc porphyrin complex Zn(II) 5,10,15,20-tetrakis(4-carboxyphenyl)porphine (ZnTCPP) through coordination bonding with metal clusters of zinc acetate (Zn[OAc]₂) was applied for synthesis of stable hybrid nanomaterial avoiding surface prefunctionalization. The X-ray powder diffraction in combination with the BET nitrogen adsorption method confirms formation of a ZnTCPP-based surface-attached metal-organic framework (SURMOF) with micropores of 1.63 nm on the MoS₂ nanosheets. Fluorescence spectroscopy confirmed Forster resonance energy transfer (FRET) between MoS₂ and ZnTCPP without contact quenching. Fluorescent trapping with terephthalic acid for hydroxyl radicals and Sensor Green for singlet oxygen was applied for studying the pathways of photodegradation of model organic pollutant 1,5-dihydroxynaphthalene (DHN) in the presence of SURMOF/MoS₂. Visible light initiates sensitization through the excitation of ZnTCPP generating singlet oxygen, whereas UV-light promotes either aerobic FRET-mediated "Z scheme" or anaerobic "Type II heterojunction" mechanisms. Owing to its multimodal photochemistry, the SURMOF/MoS₂ hybrid showed comparatively high photocatalytic activity in UV-assisted degradation of DHN (k_eff^UV = 4.0 × 10^-2 min^-1) as well as the antibacterial activity confirmed by E. coli survival test under visible light. Noncovalent self-assembly utilizing coordination bonding in SURMOFs as supramolecular adhesive to avoid surface premodification provides a basis for new types of multicomponent nanosystems with switchable functionalities by combining different 2D materials and chromophores in one hybrid structure.

Nutshells are regarded as cost-effective and abundant raw materials for producing activated carbons (ACs) for CO₂ capture, storage, and utilization. The effects of carbonization temperature and thermochemical KOH activation conditions on the porous structure as a BET surface, micropore volume, micropore width, and pore size distribution of ACs prepared from walnut (WNS) and hazelnut (HNS) shells were investigated. As a result, one-step carbonization at 900/800 °C and thermochemical KOH activation with a char/KOH mass ratio of 1:2/1:3 were found to be optimal for preparing ACs from WNS/HNS: WNS-AC-3 and HNS-AC-2, respectively. The textural properties of the WNS/HNS chars and ACs were characterized by low-temperature nitrogen vapor adsorption, XRD, and SEM methods. Dubinin’s theory of volume filling of micropores was used to evaluate the microporosity parameters and to calculate the CO₂ adsorption equilibrium over the sub- and supercritical temperatures from 216.4 to 393 K at a pressure up to 10 MPa. The CO₂ capture capacities of WNS- and HNS-derived adsorbents reached 5.9/4.1 and 5.4/3.9 mmol/g at 273/293 K under 0.1 MPa pressure, respectively. A discrepancy between the total and delivery volumetric adsorption capacities of the adsorbents was attributed to the strong binding of CO₂ molecules with the adsorption sites, which were mainly narrow micropores with a high adsorption potential. The high initial differential heats of CO₂ adsorption onto ACs of ~32 kJ/mol confirmed this proposal. The behaviors of thermodynamic functions (enthalpy and entropy) of the adsorption systems were attributed to changes in the state of adsorbed CO₂ molecules determined by a balance between attractive and repulsive CO₂–CO₂ and CO₂–AC interactions during the adsorption process. Thus, the chosen route for preparing ACs from the nutshells made it possible to prepare efficient carbon adsorbents with a relatively high CO₂ adsorption performance due to a substantial volume of micropores with a size in the range of 0.6–0.7 nm.