Search Results (24)

Pyrolysis of oily sludge (OS) faces two significant challenges, dehydration in emulsion and coke formation, which cause extra energy consumption. Targeting energy saving, this paper first reported on solar photothermal dehydration and confined catalytic pyrolysis of OS using a single material. A wood sponge loaded with carbon dots (CM-CDs) can generate heat by absorbing solar energy and promote rapid phase separation and water transport via capillary action of oil–water emulsion in OS under sunlight. Almost all free water in OS with varied content can be removed after 3 h. Hydrocarbons entered the internal space of CM-CDs instead of contacting with soil minerals, contributed to the subsequent confined catalytic pyrolysis, led to a reduction in Ea (35.61 kJ/mol), inhibited coking and caking, and yielded higher oil recovery efficiency. In addition, CDs can form hotspots to enhance pyrolytic behaviors in local regions. When the ratio of OS to CM-CDs reached 10:0.6, the recovery rate of the oil fraction through combined pyrolysis was as high as 89%, which was 17% higher than that of OS pyrolysis alone. This discovery provides a new way to solve the bottleneck problems of OS pyrolysis in the industry. Full article

The most organic-rich shales are defined in the Dobele Fm. of the Aeronian Stage of about 10 m thick in west Lithuania. This particular layer is documented in the whole Baltic Basin. Compatible shales are widely distributed in other basins referred to as similar Silurian “hot” shales. The average TOC was estimated at 6.67 wt.% (good and excellent source rock). The thermal maturity of shales was evaluated through organic geochemical techniques, including TOC determination, Rock–Eval pyrolysis, and organic petrography studies. The thermal maturity varies from T_max = 431 °C and eq.VR_o = 0.65% (early oil) to T_max = 468 °C and VR_o = 1.38% (locally up to 1.94%) (late oil and wet to dry gas generation). It is notable, most of the study area is confined to regional-scale West Lithuanian Geothermal Anomaly. Most of the geothermal features, both palaeo- and recent, recorded in lateral variation in thermal maturity of shales unravel persistence of heat flow. Locally, the Variscan tectonic activity was imprinted in thermal maturity of organic matter-rich shales (Žemaičių Naumiestis anomaly). Full article

With unique 4f electronic shells, rare earth metal-based catalysts have been attracting tremendous attention in electrocatalysis, including oxygen reduction reaction (ORR). In particular, atomically dispersed Ce/CeO₂-based catalysts have been explored extensively due to several unique features. This review article provides a comprehensive understanding of (i) the significance of the effect of Ce high-spin state on ORR activity enhancement on the Pt and non-pt electrocatalysts, (ii) the spatially confining and stabilizing effect of ceria on the generation of atomically dispersed transition metal-based catalysts, (iii) experimental and theoretical evidence of the effect of Ce³⁺ ↔ Ce⁴⁺ redox pain on radical scavenging, (iv) the effect of the Ce 4f electrons on the d-band center and electron transfer between Ce to the N-doped carbon and transition metal catalysts for enhanced ORR activity, and (v) the effect of Pt/CeO₂/carbon heterojunctions on the stability of the Pt/CeO₂/carbon electrocatalyst for ORR. Among several strategies of synthesizing Ce/CeO₂ electrocatalysts, the metal–organic framework (MOF)-derived catalysts are being perused extensively due to the tendency of Ce to readily coordinate with O- and N-containing ligands, which upon undergoing pyrolysis, results in the formation of high surface area, porous carbon networks with atomically dispersed metallic/clusters/nanoparticles of Ce active sites. This review paper provides an overview of recent advancements regarding Ce/CeO₂-based catalysts derived from the MOF precursor for ORR in fuel cells and metal–air battery applications and we conclude with insights into key issues and future development directions. Full article

Catalytic performance decline is a general issue when shaping fine powder into macroscale catalysts (e.g., beads, fiber, pellets). To address this challenge, a phenolic resin-assisted strategy was proposed to prepare porous Co/N carbon beads (ZACBs) at millimeter scale via the phase inversion method followed by confined pyrolysis. Specially, p-aminophenol–formaldehyde (AF) resin-coated zeolitic imidazolate framework (ZIF-67) nanoparticles were introduced to polyacrylonitrile (PAN) solution before pyrolysis. The thermosetting of the coated AF improved the interface compatibility between the ZIF-67 and PAN matrix, inhibiting the shrinkage of ZIF-67 particles, thus significantly improving the void structure of ZIF-67 and the dispersion of active species. The obtained ZACBs exhibited a 99.9% removal rate of tetracycline (TC) within 120 min, with a rate constant of 0.069 min⁻¹ (2.3 times of ZIF-67/PAN carbon beads). The quenching experiments and electron paramagnetic resonance (EPR) tests showed that radicals dominated the reaction. This work provides new insight into the fabrication of high-performance MOF catalysts with outstanding recycling properties, which may promote the use of MOF powder in more practical applications. Full article

Fe-N-C materials have been regarded as one of the potential candidates to replace traditional noble-metal-based electrocatalysts for the oxygen reduction reaction (ORR). It is believed that the structure of carbon support in Fe-N-C materials plays an essential role in highly efficient ORR. However, precisely designing the morphology and surface chemical structure of carbon support remains a challenge. Herein, we present a novel synthetic strategy for the preparation of porous carbon spheres (PCSs) with high specific surface area, well-defined pore structure, tunable morphology and controllable heteroatom doping. The synthesis involves Schiff-based polymerization utilizing octaaminophenyl polyhedral oligomeric silsesquioxane (POSS-NH₂) and heteroatom-containing aldehydes, followed by pyrolysis and HF etching. The well-defined pore structure of PCS can provide the confinement field for ferroin and transform into Fe-N-C sites after carbonization. The tunable morphology of PCS can be easily achieved by changing the solvents. The surface chemical structure of PCS can be tailored by utilizing different heteroatom-containing aldehydes. After optimizing the structure of PCS, Fe-N-C loading on N,S-codoped porous carbon sphere (NSPCS-Fe) displays outstanding ORR activity in alkaline solution. This work paves a new path for fabrication of Fe-N-C materials with the desired morphology and well-designed surface chemical structure, demonstrating significant potential for energy-related applications. Full article

The synthesis of methanol from CO₂ hydrogenation is an effective measure to deal with global climate change and an important route for the chemical fixation of CO₂. In this work, carbon-confined MoSe₂ (MoSe₂@C) catalysts were prepared by in situ pyrolysis using glucose as a carbon source. The physico-chemical properties and catalytic performance of CO₂ hydrogenation to yield methanol were compared with MoSe₂ and MoSe₂/C. The results of the structure characterization showed MoSe₂ displayed few layers and a small particle size. Owing to the synergistic effect of the Mo₂C-MoSe₂ heterojunction and in situ carbon doping, MoSe₂@C with a suitable C/Mo mole ratio in the precursor showed excellent catalytic performance in the synthesis of methanol from CO₂ hydrogenation. Under the optimal catalyst MoSe₂@C-55, the selectivity of methanol reached 93.7% at a 9.7% conversion of CO₂ under optimized reaction conditions, and its catalytic performance was maintained without deactivation during a continuous reaction of 100 h. In situ diffuse infrared Fourier transform spectroscopy studies suggested that formate and CO were the key intermediates in CO₂ hydrogenation to methanol. Full article

Global energy demand escalates the interest in effective and durable catalytic systems for the dry reforming of methane (DRM), a process that converts CO₂/CH₄ into H₂/CO syngas. Porous silica-supported nickel (Ni) catalysts are recognized as a promising candidate due to robust DRM activity associated with the confinement of Ni particles in the mesopores that reduces the catalyst deactivation by carbon byproduct deposits and sintering of active Ni sites. However, the small-sized pore configurations in the mesoporous catalysts hinders the fast mass transfer of reactants and products. A unique combination of the hierarchical nanostructure with macro–mesoporous features of the support is adopted to enhance the catalytic performance via the dual effect of the efficient mass transfer and minimized sintering issue. This study delves into the influence of SiO₂ geometry and pore structure on the catalytic performance of Ni-based catalysts. Three types of porous silica supports were synthesized through various methods: (a) hydrothermal-assisted sol–gel for dendritic mesoporous silica (DMS), (b) spray-pyrolysis-assisted sol–gel for spray evaporation-induced self-assembly (EISA) silica, and (c) oven-assisted sol–gel for oven EISA silica. Among the prepared catalysts the hierarchical external nanostructured Ni/DMS showed the superior CH₄ and CO₂ conversion rates (76.6% and 82.1%), even at high space velocities (GHSV = 360 L∙g⁻¹·h⁻¹). The distinctive macro–mesoporous geometry effectively prevents the sintering of Ni particles and promotes the smooth diffusion of the reactants and products, thus improving catalytic stability over extended reaction periods (24 h). This research highlights the significant impact of macro–mesoporosity revealed in DMS support catalysts on the physicochemical properties of Ni/DMS and their crucial role in enhancing DRM reaction efficiency. Full article

Nickel phosphide (Ni₂P), as an anode material for both lithium- and sodium-ion batteries, offers high theoretical specific and volumetric capacities. However, considerable challenges include its limited rate capability and low cycle stability arising from its volume change and degradation during cycling. To solve these issues, appropriate composite micro/nanoparticle designs can improve conductivity and provide confinement. Herein, we report a simple pyrolysis method to synthesize nitrogen-doped carbon-coated Ni₂P nanorod arrays (Ni₂P@NC) from nickel foam and an ionic resin as a source of carbon, nitrogen and phosphorus. The N-doped open-ended carbon shells provide Ni₂P containment, good electrical conductivity, efficient electrolyte access and the buffering of bulk strain during cycling. Consequently, as a LIB anode material, Ni₂P@NC has impressive specific capacity in long-term cycling (630 mAh g⁻¹ for 150 cycles at 0.1 A g⁻¹) and a high rate capability of 170 mAh g⁻¹ for 6000 cycles at 5 A g⁻¹. Similarly, as a SIB anode, Ni₂P@NC retains a sizable 288 mAh g⁻¹ over 300 cycles at 0.1 A g⁻¹, and 150 mAh g⁻¹ over 2000 cycles at 2 A g⁻¹. Furthermore, due to a sizable portion of its capacity coinciding with adequately low voltage, the material shows promise for high volumetric energy storage in full-cell format. Lastly, the simple synthesis method has the potential to produce other carbon-coated metal phosphides for electrochemical applications. Full article

Researchers studying heterogeneous catalysis are intrigued by single-atom catalysts (SACs) due to their ultrahigh atomic utilization. However, only a few reports on SAC-catalyzed classical organic transformations are available. In this work, atomically dispersed Pd sites are confined to a ZrO₂ hybridized N-doped carbon skeleton with a smart design. UiO-66-NH₂ is used to anchor Pd atoms by the coordination of the donor atoms including lone pairs of electrons and metal atoms. Subsequently, the in situ introduction of ZrO₂ doping is achieved using pyrolysis, which helps improve the catalytic performance by modulating the electronic state. The Pd@ZrO₂/N–C catalyst obtained from the unique design exhibits a high yield (99%) in eco-friendly media with an extremely low noble metal dosage (0.03 mol% Pd) for the Suzuki reaction. Moreover, Pd@ZrO₂/N–C remains highly active after being reused several times and possesses versatility in a variety of substrates. This strategy offers a feasible alternative to designing SACs with atomically dispersed noble metals for heterogeneous reactions. Full article

In traditional kerogen pyrolysis experiments, the effects of minerals and rock fabric on the pyrolysis products were ignored. To further clarify the role of the mineral matrix and rock fabric on hydrocarbon generation and retention, a closed anhydrous pyrolysis experiment was conducted on core plugs, powdered rock and kerogen from a clay-rich sample of Maoming oil shale within a temperature range of 312 °C to 600 °C, at a fixed pressure of 30 Mpa. The experiment’s results showed that the yields of heavy hydrocarbons (C₁₄₊) generated from the core plugs and powdered rock were obviously lower than that of kerogen, which may be caused by the retention effect of clay minerals in raw shale. The yields of gaseous hydrocarbons generated from core plugs were lower compared with powdered rock due to the retention of C₂₊ hydrocarbons by the intact rock fabric and the preferential generation of methane. Light hydrocarbon (C_6-14) yields generated from the core plugs and powdered rock were higher than kerogen, which may be the consequence of the cleavage of extraction bitumen and the interactions with kerogen. Moreover, the ratios of iso to normal paraffin (iC₄/nC₄, iC₅/nC₅) of the core plugs and powdered rock were higher than kerogen. Our experimental results show that kerogen pyrolysis in a confined system may overestimate the hydrocarbon generation potential due to the negligence of the retention effect of minerals and the rock fabric, especially in the source rocks rich in clay minerals. Full article

Platinum-based catalysts are widely used for efficient catalysis of the acidic oxygen reduction reaction (ORR). However, the agglomeration and leaching of metallic Pt nanoparticles limit the catalytic activity and durability of the catalysts and restrict their large-scale commercialization. Therefore, this study aimed to achieve a uniform distribution and strong anchoring of Pt nanoparticles on a carbon support and improve the ORR activity and durability of proton-exchange membrane fuel cells. Herein, we report on the facile one-pot synthesis of a novel ORR catalyst using metal–nitrogen–carbon (M–N–C) bonding, which is formed in situ during the ion exchange and pyrolysis processes. An ion-exchange resin was used as the carbon source containing R-N⁺(CH₃)₃ groups, which coordinate with PtCl₆²⁻ to form nanosized Pt clusters confined within the macroporous framework. After pyrolysis, strong M-N-C bonds were formed, thereby preventing the leaching and aggregation of Pt nanoparticles. The as-synthesized Pt supported on the N-doped hierarchically porous carbon catalyst (Pt/NHPC-800) showed high specific activity (0.3 mA cm⁻²) and mass activity (0.165 A mg_Pt⁻¹), which are approximately 2.7 and 1.5 times higher than those of commercial Pt/C, respectively. The electrochemical surface area of Pt/NHPC-800 remained unchanged (~1% loss) after an accelerated durability test of 10,000 cycles. The mass activity loss after ADT of Pt/NHPC-800 was 18%, which is considerably lower than that of commercial Pt/C (43%). Thus, a novel ORR catalyst with highly accessible and homogeneously dispersed Pt-N-C sites, high activity, and durability was successfully prepared via one-pot synthesis. This facile and scalable synthesis strategy for high-efficiency catalysts guides the further synthesis of commercially available ORR catalysts. Full article

Hydrazine borane (HB) is a chemical hydrogen storage material with high gravimetric hydrogen density of 15.4 wt%, containing both protic and hydridic hydrogen. However, its limitation is the formation of unfavorable gaseous by-products, such as hydrazine (N₂H₄) and ammonia (NH₃), which are poisons to fuel cell catalyst, upon pyrolysis. Previous studies proved that confinement of ammonia borane (AB) greatly improved the dehydrogenation kinetics and thermodynamics. They function by reducing the particle size of AB and establishing bonds between silica functional groups and AB molecules. In current study, we employed the same strategy using MCM-41 and silica aerogel to investigate the effect of nanosizing towards the hydrogen storage properties of HB. Different loading of HB to the porous supports were investigated and optimized. The optimized loading of HB in MCM-41 and silica aerogel was 1:1 and 0.25:1, respectively. Both confined samples demonstrated great suppression of melting induced sample foaming. However, by-products formation was enhanced over dehydrogenation in an open system decomposition owing to the presence of extensive Si-O···BH₃(HB) coordination that further promote the B-N bond cleavage to release N₂H₄. The Si-OH···N(N₂H₄) hydrogen bonding may further promote N-N bond cleavage in the resulting N₂H₄, facilitating the formation of NH₃. As temperature increases, the remaining N-N-B oligomeric chains in the porous silica, which are lacking the long-range structure may further undergo intramolecular B-N or N-N cleavage to release substantial amount of N₂H₄ or NH₃. Besides open system decomposition, we also reported a closed system decomposition where complete utilization of the N-H from the released N₂H₄ and NH₃ in the secondary reaction can be achieved, releasing mainly hydrogen upon being heated up to high temperatures. Nanosizing of HB particles via PMMA encapsulation was also attempted. Despite the ester functional group that may favor multiple coordination with HB molecules, these interactions did not impart significant change towards the decomposition of HB selectively towards dehydrogenation. Full article

The present study was conducted to investigate the potential influences of biochar in mitigating the phytotoxic effects of hexavalent chromium (Cr^VI) on the germination of wheat (Triticum aestivum L.). Biochar (JBC) was produced from Jujube (Ziziphus jujube L.) wood waste at three different pyrolysis temperatures (300 °C, 500 °C and 700 °C), which was later polymerized (JPBC) via the solution-polymerization method. Phytotoxicity of Cr^VI was induced to wheat seeds at variable Cr^VI application rates (5, 10, 20, 40 mg L⁻¹). Applied Cr^VI concentrations confined the seed germination and seedling growth in order of: 5 < 10 < 20 < 40 mg L⁻¹. The application of JBCs (0.2 g per petri plate) resulted in a 150% increase in shoot length, while dry biomass was increased by 250% with JPBCs application. Uptake of Cr^VI was significantly lower in JBC-300 (7.74 μg/seedling) and JPBC-300 (1.13 μg/seedling) treatments, as compared to control (13.24 μg/seedling), at the highest stress level (40 mg L⁻¹). Therefore, the findings of the current study showed that JBCs and JPBCs performed excellently in improving seedling growth while JPBCs performed more efficiently than pristine JBCs in mitigating Cr^VI phytotoxicity and availability. Full article

Aiming at the shortcomings of the current rock-breaking technology, a new type of high-energy expansion agent for energetic materials based on combustion-to-detonation was developed. By characterizing the basic physical and chemical properties of the high-energy expansion agent (HEEA) such as morphology, particle size distribution, and pyrolysis characteristics, the work performance of different types of high-energy expansion agents was analyzed in combination with the energy characteristics. The results showed that the relationship between the expansion work done by the gas to the outside world was W_HEEA-I > W_HEEA-II > W_HEEA-III under the same quality of HEEA combustion. The damage effect of high-temperature and high-pressure gas cracking specimens generated by deflagration of HEEA was obvious, having the rule that the disturbance damage of rock caused by low heat and high gas specific volume was smaller, and the damage degree of rock caused by high heat and low gas specific volume was larger. The mechanism of HEEA combustion and detonation in confined space is revealed, which provides a theoretical basis for the application of HEEA-cracked rock. Full article

The subject of this work is the treatment of solid waste collected from power plants using thermal plasma technology. Inductively coupled plasma (ICP), X-ray fluorescence (XRF), and energy-dispersive X-ray spectroscopy (EDX) were used to characterize the waste before and after the treatment. The results show that waste is formed essentially from carbon, but it also contains sulfur and toxic elements like lead, cadmium, zinc, and arsenic. For this reason, a plasma reactor was used to separate carbon from the heavy metals by a pyrolysis/combustion plasma system. After the plasma treatment, the mass of the waste was reduced by more than 85% and the metals were collected in the filter bag. A computer code was used to study the toxic element volatility during the treatment. With this code, the effects of plasma temperature, confinement matrix, and the composition of the carrier gas on the volatility of lead and arsenic were determined. The code results show that arsenic remains in the liquid phase for temperatures less than 2000 K, whereas for temperatures beyond 2100 K, arsenic becomes very volatile. For lead, any increase in temperature increases its vaporized quantity and its vaporization speed. The addition of oxygen in the carrier gas leads to the heavy metal incorporation in the confinement matrix. The increase of the quantity of Ba in the containment matrix strengthens the confinement of as in the matrix. Full article