Ni-based catalysts have been extensively investigated for lignin hydrogenation; however, they often exhibit limited phenol selectivity and poor catalytic stability. To address these challenges, we introduced Cu as a promoter, resulting in the development of NiCu/ZSM-5 catalysts with significantly enhanced phenol selectivity and durability. Characterization studies revealed that Cu species form an alloy structure with Ni, which effectively suppresses the sintering of Ni nanoparticles during the catalytic process, thereby maintaining consistent performance over multiple reaction cycles. Furthermore, the Cu-Ni alloy demonstrated improved hydrogen activation capability while reducing overall H2 uptake, leading to a marked increase in phenol selectivity compared to the Cu-free Ni/ZSM-5 catalyst. As a result, the Ni1Cu1/ZSM-5 (Ni/Cu molar ratio = 1:1) catalyst achieved a lignin conversion of 69.8% and a phenol selectivity of 84.4%, with negligible performance degradation over 8 cycles. The strategy presented in this work may offer an effective approach for enhancing the performance of industrial catalysts in lignin upgrading processes.

The study of thermal developments of heavy oil feedstock, vacuum residue in particular, is a relevant factor for the development of technologies for the processing and production of petroleum products. This paper investigates the process of thermal decomposition of the vacuum residue in the manufacturing of catalyst and polymer material using thermal analysis methods, including thermogravimetric analysis (TGA) in isothermal and dynamic modes. Particular attention is paid to the measurement of kinetic parameters of thermolysis using model and non-model methods, which allows us to assess the output power and other kinetic characteristics of decomposition. The results obtained can be used for the development of new oil refining technologies for significantly increasing the efficiency and safety of processes. During the course of this study, experimental and theoretical activation energy values were obtained for the vacuum residue without a catalyst (experimentally: 91.54 kJ mol−1/theoretically: 91.35 kJ mol−1) and a sample with the presence of a catalyst (experimentally: 89.68 kJ mol−1/theoretically: 90.87 kJ mol−1). The reduction in activation energy in the presence of the catalyst confirms its catalytic activity and potential for processing heavy hydrocarbon feedstock.

A spherical CuO-Bi2O3-MgO/SiO2 catalyst was prepared using the coprecipitation-gel method. The study investigated the influence of the MgO/SiO2 ratio on the catalyst structure and the activity of the catalyst in the preparation of 1,4-butanediol from formaldehyde acetylenation. The activity and filtration performance of the catalyst were compared with commercial samples. The study found that different MgO/SiO2 ratios not only changed the size of CuO particles, the orientation of crystal faces, the specific surface area, and the pore distribution in the catalyst, but also adjusted the interaction between CuO and SiO2. In addition, different MgO/SiO2 ratios could significantly alter the structure of the catalyst and enhance its activity, with the highest activity achieved when the MgO/SiO2 ratio was 1:3. Experimental results showed that the spherical CuO-Bi2O3-MgO/SiO2 catalyst in this study achieved a selectivity of 96.3% and a conversion rate of 94.0% when reacting with formaldehyde at a concentration of 38 wt% for 12 h. The catalyst outperformed commercial samples in terms of activity and had the same strength level and better filtration separation performance as commercial samples.

The scientific novelty of this study lies in a comprehensive analysis of the physical and chemical properties of brown coal of the Kuznetsk deposit using modern research methods. Data on elemental composition, ash content, moisture and volatile matter yield of this coal are systematized and presented. Particular attention was paid to the study of the influence of functional groups on the reactivity of coal, which had not previously been studied in such a detailed form for this deposit. This research uniquely unveils and details the chemical structures of humic acids, offering a more comprehensive understanding of their makeup and functional aspects. The resulting activation energies ranged from 35.65 to 143.9 kJ/mol, with an average of approximately 73.3 kJ/mol, indicating the moderate thermal stability of humic acids derived from the feedstock. Optimal extraction conditions were achieved by treating brown coal from the Kuznetsk deposit with a 4% NaOH solution at 80°C for 2 hours, yielding up to 7% humic acids. Ultrasonic treatment enhanced the physicochemical characteristics of the coal, particularly by increasing the number of oxygen-containing functional groups, as confirmed by IR spectroscopy. The presence of hydroxyl groups was observed in the 3800–3550 cm⁻¹ range, while absorption bands between 1600–1250 cm⁻¹ indicated aromatic structures, suggesting a significant content of stable carbon bonds. The coal exhibited a microporous structure, with pore diameters around 5 nanometers, supporting its high adsorption capacity for gases and liquids. Additionally, nanoparticles approximately 1 nanometer in size were identified, possibly originating from organic matter decomposition or interactions between coal and mineral components, potentially affecting its reactivity. Thus, the research results obtained are a significant contribution to the field of coal chemistry and ecology, and can also serve as the basis for further research and development in the field of the use of humic acids as environmentally friendly additives and sorbents.

This study presents the synthesis and comparative characterization of humic acids extracted from brown coals of the Kuznetsk and Kumyskuduk deposits in Kazakhstan. Advanced analytical techniques, including infrared (IR) spectroscopy, elemental analysis, thermogravimetric (TGA/DSC) analysis, scanning electron microscopy (SEM), UV-Vis spectroscopy, and band gap analysis, were employed to evaluate their physicochemical properties. The results revealed marked differences in elemental composition, functional group distribution, thermal stability, surface morphology, and optical properties, reflecting the distinct geological origins of each deposit. Notable variations in pH, titratable acidity, and the ratio of carboxyl to phenolic hydroxyl groups suggest differences in buffering capacity and sorption behavior. The higher concentrations of carboxyl and hydroxyl groups in some samples enhance their potential for complexation and adsorption processes. This comparative analysis highlights the potential of these humic acids for use in agriculture, environmental remediation, and wastewater treatment. The findings contribute to a deeper understanding of how geological factors influence the structural and functional characteristics of humic substances, broadening their scope of practical applications and guiding future material development.

Understanding hydrogen activation is crucial for improving the performance of direct coal liquefaction (DCL) which is essential for the clean, efficient conversion of coal to fuel oils and aromatic chemicals. Three hydrogen sources are involved in DCL: solvent hydrogen (SH), dissolved hydrogen that reacts directly (DHD), and dissolved hydrogen that reacts through a solvent (DHS). Quantitatively studying DHS is challenging because it is generated through the dehydrogenation of hydrogen-donor solvents produced via the hydrogenation of gas-phase H2 and solvents. This research establishes for the first time a quantitative method for determining DHS consumption (DHSC) based on protium- and deuterium-nuclear-magnetic-resonance results for solvents after isotope-tracer reactions. Comparative experiments and quantum-chemical calculations were performed to confirm the method’s reliability. The isotope-tracer method showed that DHSC accounts for < 7 % of the total hydrogen consumption under catalysis with ferric stearate, nickel stearate, or molybdenum 2-ethylhexanoate, while DHD consumption accounts for > 50 %. Thus, DHD, rather than DHS, is the primary hydrogen source for catalytic activation. Furthermore, the comparative experiments also showed that hydrogen consumption is greater for one hydrogen source than for the coexistence of the three hydrogen sources, indicating competition among the three sources. The quantum-chemical calculations showed that the competitiveness among the three sources follows the order of DHS < SH < DHD, this agrees with the order of hydrogen consumption in the isotope-tracer experiments. This study quantitatively reveals the mechanism responsible for hydrogen activation by catalysts and provides a scientific basis for optimization and mutual matching of solvents and catalysts.

The paper studied the effect of high-voltage short-pulse electrohydraulic discharge (HVSPED) on the processes of catalytic cracking of oil sludge in order to increase the yield of light hydrocarbon fractions. A set of laboratory experiments was carried out varying the key parameters of HVSPED-discharge voltage, capacitance of capacitor banks and processing time. As a catalyst, the developed nanocomposite catalyst bentonite was used, with nickel packed. The optimal electrophysical parameters of oil sludge treatment by HVSPED were determined, providing the maximum yield of gasoline and kerosene fractions. The effectiveness of HVSPED treatment of oil sludge in the presence of a catalyst was confirmed by DTA-thermogravimetric analysis and chromatographic-mass spectral analysis of the light and middle fractions of the hydrogenate. The proposed approach made it possible to enhance the resource and energy efficiency of oil sludge processing using HVSPED, demonstrating high potential for further industrial application

Carbon materials combining ultra-micropores and long-range graphitic domains are highly desired for enhancing their capacitive deionization (CDI) properties, but conventional fabrication strategies struggle with this trade-off contradiction. Herein, a novel pitch molecular design strategy is developed, combining diphenylurea-induced thermal polycondensation with potassium hydrogen phthalate-assisted activation. As-obtained carbon (DMPC) exhibits ultra-microporosity (0.8 nm) and order-in-disordered pseudographitic domains. Benefiting from systematic engineering of tailored pore size modulation, the active sites of nitrogen configurations on the micropore lattice scaffolds are significantly enhanced, reducing charge transfer resistance and increasing ion transfer/ storage capacity. The symmetric DMPC electrode has comprehensive CDI performance, showcasing a salt adsorption capacity of 42.4 mg g- 1 at an average desalination rate of 2.64 mg g- 1 min- 1 and a charging efficiency of 63.3 % at 1.4 V in a 500 mg L- 1 NaCl solution. Notably, the good cycling durability and antioxidant mechanism of DMPC are demonstrated in mixed salt solutions. This study sheds light on the potential of molecular design engineering of pitch to tailor porosity and graphitization, paving a new path in advanced carbon electrodes for capacitive deionization.

The cleavage of covalent bonds and the generation of radicals play a crucial role in product distribution during direct coal liquefaction (DCL). This paper systematically investigates the mechanisms of covalent bond cleavage and the behavior of free radical generation for Naomaohu (NMHC) and Shangwan (SWC) coals during the DCL process. The concentrations of eight typical covalent bonds in raw coal and in the solid products Asphaltene (ASP) and Residue (Re) were quantified using 13C NMR, while information on free radicals was obtained through GC-MS and GC analyses. The results indicate that NMHC contains a higher concentration of easily cleavable covalent bonds, such as Cal-O and Cal-Cal, endowing it with superior reactivity compared to SWC. During the heating process, the breaking rate of Cal-Cal bonds in the ASPNMHC and ReNMHC being 3.0 times higher than those in SWC. Additionally, the proportion of aromatic radicals in OilNMHC is 19.1 % lower than that in OilSWC. This study systematically investigates the differences in reactive behavior between NMHC and SWC, emphasizing the core chemical reactions involved in DCL. It provides a theoretical foundation for developing an efficient direct liquefaction process for NMHC, oil-rich coal.

To address limited desalination capacity and insufficient charge efficiency for carbon materials in capacitive deionization (CDI), a solid-liquid synergistic oxidation strategy of potassium pertechnetate (VI) for pitch was proposed to construct porous carbon with a reasonable pore structure and high reactive surface. On the one hand, K2FeO4 2 FeO 4 is first utilized for the solid-phase oxidation (SPO) of pitch by a high-energy ball mill, introducing rich oxygen-containing groups such as ether bonds. Meanwhile, dehydro-condensation reactions occurred during SPO, resulting in the formation of the oxidized pitch with a high degree of condensation. Importantly, the pyrolysis yield of the oxidized pitch is as high as 46.9 % at 800 degrees C, almost twice that of the pristine pitch, meaning that the oxidized pitch with high polymer degree and rich C-O bridge bonds facilitates the carbon fixation and emission reduction during carbonization. On the other hand, the self-oxidation of K2FeO4 2 FeO 4 in aqueous solution forms bifunctional activators (KOH and Fe(OH)3) 3 ) for the preparation of pitch-based porous carbon. Benefiting from the crosslinking structure of oxidized pitch and the multi-effective activation, the prepared porous carbon (H-CBPF) exhibits a robust layered stacking topology with a high surface area and oxygen content. Thereby, it can deliver an excellent salt adsorption capacity (SAC) of 22.1 mg g- 1 with an average desalination rate of 1.89 mg g- 1 green and economical route for the preparation of pitch-derived porous carbon for high-performance CDI. min- 1 and a high charge efficiency of 85 % at 1.2 V in 500 mg L-1 NaCl solution. This work opens up a

In order to evaluate the possibility of using different catalysts prepared for the hydrogenation process of primary coal tar, the method of differential thermal analysis was used, which allows to determine the kinetic parameters of thermal destruction, such as the rate constant, activation energy, and pre -exponential multiplier. The effect of catalysts on characteristics of mass loss during heating of "Shubarkol Komir" JSC primary coal tar at a constant speed (20 K/min) in a nitrogen medium has been considered. Microsphere, NiO/microsphere, CoO/microsphere, chrysotile and NiCo/chrysotile have been taken as catalytic additives. In the presence of the catalysts, the rate of thermal destruction of primary coal tar increases in the following order: CoO/microsphere < NiO/microsphere < NiCo/chrysotile. While microsphere catalysts extend the range of thermal destruction, chrysotile catalysts lead to the rapid completion of the destruction process. This fact is characterized by the formation of bonds between catalytic additives and primary coal tar. It is important to determine such parameters that affect on the activation energy and macrokinetics of the thermal decomposition process for prediction of catalyst activity during hydrogenation of heavy hydrocarbon raw materials.

Three lignites were subjected to sequential thermal dissolution using cyclohexane, methanol, and ethanol as the solvent to acquire soluble fractions (SFs). Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC x GC/TOF MS) was used to separate and reveal complex molecular composition of SFs. Low polar compounds such as chain alkanes (CAs) and arenes were enriched by cyclohexane. Strong polar compounds like phenols were concentrated by methanol, and partial phenols and CAs were also detected in the ethanol extracts. Meanwhile, organic nitrogen compounds (ONCs) and organic sulfur compounds (OSCs) such as pyridines, quinolines and thiophenes were identified in SFs. In all SFs, pyridines have the highest relative abundance, followed by quinolines compared with other ONCs, and thiophenes were only detected in cyclohexane and methanol SFs. In addition, halogen-containing compounds reflecting the geochemical characteristics of lignite were also detected, and their total relative abundances were 0.544%, 1.591% and 5.101% in the SFs of Shengli (SL), Xiheishan (XHS), and Xiaolongtan (XLT), respectively, which provided evidence for the evolution of coal. Two unsupervised analysis methods, hierarchical cluster analysis and principal components analysis, were efficient in clustering components according to molecular characteristics, and visualized detailed similarities and differences among the compounds in SFs.

The temperature dependence of dynamic viscosity was calculated on the basis of a new cluster-association equation, which was derived within the framework of the concept of chaotic particles. It was shown that the degree of cluster association naturally decreases with an increase in temperature, on average corresponding to the arrangement of three to four cluster particles in the association. For the first time, the values of the activation energy per monomer were obtained when assigning the activation energy to the average number of clusters.

Directly converting lignite into arenes as commodity chemicals and drop-in fuels is a highly desirable target for researchers. However, this is severely limited by the presence of stable inter unit C-O linkages in lignite. Herein, a highly active catalyst, Co-MoS2, has been designed and prepared to be used for the selective catalytic cleavage of inter unit C-O bridged bonds (BBs) in the conversion of Naomaohu (NMH), a lignite, to yield arenes. Both catalytic hydrogenation conversion (CHC) and thermal dissolution (a non-catalytic process, named NCHC) of NMH were conducted using n-hexane as the solvent. The soluble fractions from the first stage of NCHC (SFNCHC-1) and CHC (SFCHC-1), as well as the second stage of NCHC (SFNCHC-2) and CHC (SFCHC-2) were obtained using the same solvent. After the first-stage catalytic treatment, the relative contents of arenes and alkanes in SFCHC-1 increased by 16.7% and 9.3%, respectively, compared to those in SFNCHC-1, and the relative content of oxygen-containing compounds (OCCs), such as alcohols, phenols, esters, ketones, acids, and furans, decreased by 13.2%. For the second-stage conversion, the relative contents of arenes and alkanes in SFCHC-2 were 53.5% and 15.5% higher than those in SFNCHC-2, and the relative contents of OCCs was only 6.6% in SFCHC-2. The catalytic mechanisms of cleavage of C-O BBs and deoxygenation were proposed based on the CHC of model compounds and density functional theory (DFT) calculation. The adsorption of OCCs and the activation of released hydrogen radical (H·) by Co-MoS2, followed by H· addition to the carbon atom connected to oxygen in C-O BBs and oxygen-containing functional groups, are crucial for the cleavage of C-O BBs and formation of deoxygenated compounds, particularly arenes.

Simulated wastewater samples, representative of coal chemical industry and comprising major constituents such as phenol, p-cresol, o-cresol, and naphthalene, were subjected to treatment in a range of catalytic ozonation systems. To prepare the catalysts for ozonation, three series of metal oxides, iron oxides, manganese oxides, and cerium oxides, were manufactured onto the surface of gamma-Al2O3 support in varying loadings. The determination of the optimal loading amount for each catalyst was based on the observed removal efficiency of chemical oxygen demand (COD) in phenol-containing aqueous solution. Primary small molecular organic acids formed in the aqueous solution during the degradation of phenol were analyzed by ion chromatography. The decomposition of ozone without catalyst can directly oxidize phenol, and catalytic ozonation can reach the same goal through the generation of center dot OH. The synergy effects between ozone and the catalysts facilitate the production of highly reactive oxidizing species, leading to more efficacious degradation of phenol and an increased total concentration of organic acids till 37.8 mg/L. Radical capture experiments revealed that the generation of center dot OH within the catalyzed ozonation system is associated with the presence of oxygen defects on the catalyst's surface, which significantly influenced the catalytic efficacy during the ozonation process. A loading of 20 %CeO2 on gamma-Al2O3 support exhibited the best COD removal rate as high as 90 % due to the increased availability of lattice oxygen participating in catalytic ozonation. Thus, the methodology built for the optimization of ozonation catalyst is proven a promising way to prepare candidate catalyst for the treatment of wastewater from coal chemical industry.

Coal and residuum are first co-pyrolyzed, and then hydrogenated into small molecule products during co-liquefaction. Therefore, clarifying influence of residuum on coal pyrolysis performance is an important thermochemical basis for regulating the process. The co-pyrolysis behavior of atmospheric residuum (AR) and Naomaohu coal (NMH) were investigated by TG, TG-FTIR and distributed activation energy model. The results showed that the peak temperature of the maximum rate of weight loss for the co-pyrolysis process was reduced by 7 °C compared with the theoretical value calculated by weighted average of AR and NMH pyrolysis alone, while the weight loss increased by 3%, the average activation energy decreased by 23.6 kJ/mol. In addition, the peak area of alkyl O-containing functional groups such as alcohols and ethers increased, whereas those of CO and CO2 decreased, suggesting that AR had a positive effect on NMH pyrolysis. Meanwhile, alkyl radicals from AR decomposition would combine with O-containing radicals generated from coal pyrolysis, thus resulting in a decrease of CO and CO2 by inhibiting breakage of carboxyl groups. This work will provide a scientific evaluation basis for revealing the influence of residuum on composition of coal liquefaction product during co-liquefaction.

The CuO-Bi2O3/MgAl2O4 catalyst was synthesized via one-pot synthesis and used to catalyze formaldehyde (HCHO) ethynylation. Coprecipitation using Cu2+, Bi3+, Mg2+, and Al3+ nitrates and NaOH generated Cu and Bi oxides and spinel MgAl2O4 phase. The catalyst precursor was calcined at 450 °C. The catalytic performance of CuO-Bi2O3/MgAl2O4 in the synthesis of 1,4-butynediol via HCHO ethynylation was investigated. The presence of a new spinel phase enhanced the acid-base properties on the catalyst surface and prevented the aggregation of CuO particles. These properties resulted in improved CuO dispersion during calcination and CuO particle growth suppression, affording smaller CuO crystals. The MgAl2O4 support facilitated the reduction of Cu2+ to Cu+ and formation of abundant active species during the reaction. The catalyst exhibited abundant weakly basic, fewer strongly basic, and least acidic sites, which facilitated the adsorption of HCHO and acetylene. The catalytic performance of CuO-Bi2O3/MgAl2O4 demonstrated 97 % conversion and 80 % selectivity after the online monitoring of the ethynylation reaction for 6 h. The leaching of Cu during the reaction, as analyzed by inductively coupled plasma spectroscopy, was extremely low. Moreover, conversion and selectivity did not substantially change after eight cycles. In addition, the catalyst exhibited superior activity and long-term stability in the ethynylation reaction.

催化剂是降低煤直接液化苛刻反应条件、提高液化油产率的重要因素.以新疆俄霍布拉克煤田次烟煤为碳源,以Ni(NO3)2水溶液为镍源,采用一步原位负载煅烧还原法,制备了 Ni负载量分别为7％,8％,15％和22％(质量分数)的Ni/煤基活性炭(Ni/coal-based activated car-bon,Ni/CAC)催化剂.以新疆准东西沟煤田褐煤为煤样,通过液化实验,考察了 Ni负载量对Ni/CAC的形貌和结构特征、液化效果及液化油组成的影响.结果表明:Ni以单质负载于CAC孔壁,随着其负载量的增加,晶粒尺寸迅速增加,晶粒比表面积和分散度以及催化剂的比表面积和孔体积均减小.准东西沟褐煤液化实验表明,随着Ni负载量的增加,转化率和油产率均呈开口向下抛物线变化,在8％的Ni负载量时,均达到最大值,分别为89.50％和75.69％;总氢耗为3.51 g(H2)/100 g(煤),其中,气相氢耗为2.00 g(H2)/100 g(煤),占总氢耗的57％.液化油的GC-MS分析表明,不同Ni负载量的四种试样的液化油中,烷烃含量均最高,约占40％;含氧化合物含量为20％～30％,以酚类为主;芳烃含量也为20％～30％,以单环芳烃和双环芳烃为主;含N,S等化合物含量为8％～11％.随着Ni负载量的增加,烷烃含量增加幅度较大,含氧化合物含量减少,芳烃等其他化合物含量变化不大.

Cisplatin is a well-known platinum-based chemotherapy medication that is widely utilized for some malignancies. Despite the direct cytotoxic consequences of cisplatin on tumor cells, studies in the recent decade have revealed that cisplatin can also affect different cells and their secretions in the tumor microenvironment (TME). Cisplatin has complex impacts on the TME, which may contribute to its anti-tumor activity or drug resistance mechanisms. These regulatory effects of cisplatin play a paramount function in tumor growth, invasion, and metastasis. This paper aims to review the diverse impacts of cisplatin and nanoparticles loaded with cisplatin on cancer cells and also non-cancerous cells in TME. The impacts of cisplatin on immune cells, tumor stroma, cancer cells, and also hypoxia will be discussed in the current review. Furthermore, we emphasize the challenges and prospects of using cisplatin in combination with other adjuvants and therapeutic modalities that target TME. We also discuss the potential synergistic effects of cisplatin with immune checkpoint inhibitors (ICIs) and other agents with anticancer potentials such as polyphenols and photosensitizers. Furthermore, the potential of nanoparticles for targeting TME and better delivery of cisplatin into tumors will be discussed.