Search Results (45)

In this study, a novel activated carbon (AC) (AC-Ba(OH)₂) was synthesized through a three-step process (including hydrothermal carbonization (at 250 °C), alkali activation by Ba(OH)₂, and pyrolysis (at 850 °C)), from Plane tree fruits (PTFs). By using various experimental methods for material characterization, it was established that the resulting material possesses a variety of oxygen functional groups, rich in alkaline earth oxides (BaO/CaO), SiO₂, consisting of graphitized carbon with graphene structures. A detailed kinetic and thermodynamic analysis of AC-Ba(OH)₂ thermal restoring was also carried out. Thermodynamic analysis revealed the existence of a true thermodynamic compensation effect (TCE) during restoration. Restoration was controlled by entropy, where experimental temperatures are above the iso-entropic temperature, i.e., the temperature where contributions of enthalpy and entropy to activation free energy are balanced. Kinetic modeling has shown that restoration allows carbon material to be significantly modified by removing oxygen-containing groups via diffusion, changing active sites on the surface, and preparing material for catalyst support. CaO and SiO₂ act as catalysts, while BaO alters graphene surface properties. Isothermal prediction tests have shown an extremely high long-term stability of modified AC-Ba(OH)₂, supporting an elevated activity, selectivity, and lifetime, as well. The restoring process resulted in an energy consumption of 0.762 kWh, which is equivalent to the reactivation of AC with a lower specific surface area. Manufactured AC and its thermally modified counterpart can be used as both a catalyst support and catalyst for reforming processes, such as methanol synthesis, biogas purification, and dry reforming of methane. Full article

The development of highly active, thermally stable, and low-CO-selective catalysts is critical for practical methanol steam reforming (MSR) to produce high-purity hydrogen for fuel cell applications. In this work, a series of Mn–Cu/Al₂O_x catalysts with varying Mn/Cu/Al molar ratios were synthesized via co-precipitation and systematically investigated to establish the relationship between composition, structure, and catalytic performance. XRD analysis revealed the formation of spinel-type CuAl₂O₄ and MnAl₂O₄ phases, with Mn preferentially occupying octahedral B-sites to form MnAl₂O₄, thereby inducing lattice distortion and inhibiting grain growth. SEM and TEM–EDS mapping confirmed uniform elemental distribution and a porous nanoscale morphology, while H₂-TPR results suggested that increasing the Mn/Cu ratio strengthens Mn–Cu interactions, shifts Cu²⁺ reduction to higher temperatures, and enhances Cu dispersion (up to 26.11 m²/g). XPS analysis indicated that Mn doping enriches Mn³⁺ species and facilitates oxygen vacancy formation, which promotes water–gas shift (WGS) activity and suppresses CO formation. Catalytic testing (240–300 °C) showed that Mn₂Cu₂Al₄O_x achieved the highest methanol conversion while maintaining low CO selectivity; in contrast, reducing the Mn/Cu ratio increased CO selectivity, detrimental to hydrogen purification. Stability tests under continuous steam exposure for 24 h demonstrated minimal activity loss (~2%) and negligible increase in CO selectivity (<1%), confirming excellent hydrothermal stability. The results indicate that tailoring the Mn/Cu ratio optimizes the balance between redox properties and metallic Cu dispersion, offering a promising route to design low-CO, durable catalysts for on-site hydrogen generation via MSR. Full article

The growing demand for air connectivity, coupled with the forecasted increase in passengers by 2040, implies an exigency in the aviation sector to adopt sustainable approaches for net zero emission by 2050. Sustainable Aviation Fuel (SAF) is currently the most promising short-term solution; however, ensuring its overall sustainability depends on reducing the life cycle carbon footprints. A key challenge prevails in hydrogen usage as a reactant for the approved ASTM routes of SAF. The processing, conversion and refinement of feed entailing hydrodeoxygenation (HDO), decarboxylation, hydrogenation, isomerisation and hydrocracking requires substantial hydrogen input. This hydrogen is sourced either in situ or ex situ, with the supply chain encompassing renewables or non-renewables origins. Addressing this hydrogen usage and recognising the emission implications thereof has therefore become a novel research priority. Aside from the preferred adoption of renewable water electrolysis to generate hydrogen, other promising pathways encompass hydrothermal gasification, biomass gasification (with or without carbon capture) and biomethane with steam methane reforming (with or without carbon capture) owing to the lower greenhouse emissions, the convincing status of the technology readiness level and the lower acidification potential. Equally imperative are measures for reducing hydrogen demand in SAF pathways. Strategies involve identifying the appropriate catalyst (monometallic and bimetallic sulphide catalyst), increasing the catalyst life in the deoxygenation process, deploying low-cost iso-propanol (hydrogen donor), developing the aerobic fermentation of sugar to 1,4 dimethyl cyclooctane with the intermediate formation of isoprene and advancing aqueous phase reforming or single-stage hydro processing. Other supportive alternatives include implementing the catalytic and co-pyrolysis of waste oil with solid feedstocks and selecting highly saturated feedstock. Thus, future progress demands coordinated innovation and research endeavours to bolster the seamless integration of the cutting-edge hydrogen production processes with the SAF infrastructure. Rigorous techno-economic and life cycle assessments, alongside technological breakthroughs and biomass characterisation, are indispensable for ensuring scalability and sustainability. Full article

Ni-based catalysts have been widely used in catalytic reactions by researchers due to their advantages such as abundant resources, high catalytic activity and lower prices than precious metals. However, the problems of easy agglomeration and poor dispersion of Ni-based catalysts have hindered their large-scale application. Therefore, it is necessary to select a suitable preparation method to reduce the agglomeration of the catalyst and improve its dispersion. In this paper, the Ni-NiAl₂O₄/tourmaline composite material was prepared by using the microwave hydrothermal reduction method. The most favorable conditions for preparing NiAl₂O₄/tourmaline are as follows: using TEOA as the additive, the microwave hydrothermal temperature is 220 °C, the calcination temperature is 800 °C, and the addition amount of tourmaline is 7.4 wt.%. NiAl₂O₄ has a good dispersion over the surface of tourmaline support and the optimal NiAl₂O₄/tourmaline catalyst exhibits a specific surface area of 106.5 m²/g. Metallic nickel was reduced at 650 °C to further obtain Ni-NiAl₂O₄/tourmaline composites. Finally, the Ni-NiAl₂O₄/tourmaline composites showed significantly improved catalytic dry reforming of methane (DRM) activity compared to Ni-NiAl₂O₄ sample under low-temperature conditions (500–600 °C), meaning that the tourmaline carrier could effectively optimize the low-temperature catalytic performance of Ni-NiAl₂O₄. Full article

The engineering of pore structures has great significance in the development of high-performance carbon-based supercapacitor electrode materials. Herein, we have successfully transformed jujube pits into hierarchical porous carbon (HJPC-4) with excellent capacitive properties via a unique hydrothermal–carbonization–activation strategy. Hydrothermal pretreatment is essential to regulate the supermesoporous and macroporous structure of samples and their superior electrochemical performances. Owing to the large ion-accessible, remarkable supermesoporous and macroporous pore volume, HJPC-4 exhibited ultra-high specific capacitance (6 M KOH: 316 F g⁻¹ at 1 A g⁻¹; EMIMBF₄: 204 F g⁻¹ at 1 A g⁻¹), excellent rate performance (6 M KOH: 231 F g⁻¹ at 100 A g⁻¹; EMIMBF₄: 154 F g⁻¹ at 30 A g⁻¹), outstanding cycling stability (6 M KOH: the retention rate is 92.11% after 60,000 cycles at 10 A g⁻¹; EMIMBF₄: the retention rate is 80% after 10,000 cycles at 5 A g⁻¹), and ultimate energy/power density up to 91.09 Wh kg⁻¹/24.25 kW kg⁻¹ in EMIMBF₄ two-electrode systems. This work presents unique insights into the effect of the pore structure of carbon-based materials on their capacitive energy storage. Full article

The water–gas shift (WGS) reaction is one of the most significant reactions in hydrogen technology since it can be used directly to produce hydrogen from the reaction of CO and water; it is also a side reaction taking place in the hydrocarbon reforming processes, determining their selectivity towards H₂ production. The development of highly active WGS catalysts, especially at temperatures below ~450 °C, where the reaction is thermodynamically favored but kinetically limited, remains a challenge. From a fundamental point of view, the reaction mechanism is still unclear. Since specific nanoshapes of CeO₂-based supports have recently been shown to play an important role in the performance of metal nanoparticles dispersed on their surface, in this study, a comparative study of the WGS is conducted on Pt nanoparticles dispersed (with low loading, 0.5 wt.% Pt) on CeO₂ and gadolinium-doped ceria (GDC) supports of different nano-morphologies, i.e., nanorods (NRs) and irregularly faceted particle (IRFP) CeO₂ and GDC, produced by employing hydrothermal and (co-)precipitation synthesis methods, respectively. The results showed that the support’s shape strongly affected its physicochemical properties and in turn the WGS performance of the dispersed Pt nanoparticles. Nanorod-shaped CeO_2,NRs and GDC_NRs supports presented a higher specific surface area, lower primary crystallite size and enhanced reducibility at lower temperatures compared to the corresponding irregular faceted CeO_2,IRFP and GDC_IRFP supports, leading to up to 5-fold higher WGS activity of the Pt particles supported on them. The Pt/GDC_NRs catalyst outperformed all other catalysts and exhibited excellent time-on-stream (TOS) stability. A variety of techniques, namely N₂ physical adsorption–desorption (the BET method), scanning and transmission electron microscopies (SEM and TEM), powder X-ray diffraction (PXRD) and hydrogen temperature programmed reduction (H₂-TPR), were used to identify the texture, structure, morphology and other physical properties of the materials, which together with the in situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) and detailed kinetic studies helped to decipher their catalytic behavior. The enhanced metal–support interactions of Pt nanoparticles with the nanorod-shaped CeO_2,NRs and GDC_NRs supports due to the creation of more active sites at the metal–support interface, leading to significantly improved reducibility of these catalysts, were concluded to be the critical factor for their superior WGS activity. Both the redox and associative reaction mechanisms proposed for WGS in the literature were found to contribute to the reaction pathway. Full article

Hydrogen is a clean-burning fuel with water as its only by-product, yet its widespread adoption is hampered by logistical challenges. Liquid organic hydrogen carriers, such as alcohols from sustainable sources, can be converted to hydrogen through aqueous-phase reforming (APR), a promising technology that bypasses the energy-intensive vaporization of feedstocks. However, the hydrothermal conditions of APR pose significant challenges to catalyst stability, which is crucial for its industrial deployment. This review focuses on the stability of catalysts in APR, particularly in sustaining hydrogen production over extended durations or multiple reaction cycles. Additionally, we explore the potential of ultrasound-assisted APR, where sonolysis enables hydrogen production without external heating. Although the technological readiness of ultrasound-assisted or -induced APR currently trails behind thermal APR, the development of catalysts optimized for ultrasound use may unlock new possibilities in the efficient hydrogen production from alcohols. Full article

In this entry, the possibility of the implementation of a biorefinery based on multiple raw materials (from agricultural wastes, vegetable oils, etc.) is covered, pointing out the available technology to interconnect different processes so that the atom economy of the process is as high as possible, reducing the environmental impact and improving the efficiency of the energy or products obtained. For this purpose, this model is based on previous works published in the literature. The role of biorefineries is becoming more and more important in the current environmental scenario, as there is a global concern about different environmental issues such as climate change due to GHG emissions, among others. In this sense, a biorefinery presents several advantages such as the use of natural raw materials or wastes, with high atom economy values (that is, all the products are valorized and not released to the environment). As a consequence, the concept of a biorefinery perfectly fits with the Sustainable Development Goals, contributing to the sustainable growth of different regions or countries, regardless of their stage of development. The aim of this entry is the proposal of a biorefinery based on multiple raw materials, using different technologies such as transesterification to produce both biodiesel and biolubricants, steam reforming to produce hydrogen from glycerol or biogas, hydrothermal carbonization of sewage sludge to produce hydrochar, etc. As a result, these technologies have potential for the possible implementation of this biorefinery at the industrial scale, with high conversion and efficiency for most processes included in this biorefinery. However, there are some challenges like the requirement of the further technological development of certain processes. In conclusion, the proposed biorefinery offers a wide range of possibilities to enhance the production of energy and materials (hydrogen, biodiesel, biolubricants, different biofuels, hydrochar, etc.) through green technologies, being an alternative for petrol-based refineries. 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

The large Dongtangzi Zn-Pb deposit is located in the southwest of the Fengxian–Taibai (abbreviated as Fengtai) ore cluster in the west Qinling orogen. The origin of the deposit is controversial, positing diverse genesis mechanisms such as sedimentary-exhalative (SEDEX), sedimentary-reformed, and epigenetic-hydrothermal types. This study combines systematic ore geology observations with high-precision Rb-Sr and Sm-Nd ages of 211 Ma and in situ S-Pb isotopes to constrain the timing and origin of mineralization. In situ S-Pb isotopic studies show that the sulfide ores display a narrow range of δ³⁴S values from 1.1‰ to 10.2‰, with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios of 18.07 to 18.27, 15.64 to 15.66, and 38.22 to 38.76, respectively. On the other hand, pyrites of the sedimentary period and the granite porphyry dike have δ³⁴S values ranging from 15.8 to 21.4‰ and from 2.1 to 4.3‰ (with ²⁰⁶Pb/²⁰⁴Pb ratios of 18.09 to 18.10, ²⁰⁷Pb/²⁰⁴Pb ratios of 15.59 to 15.61, and ²⁰⁸Pb/²⁰⁴Pb ratios of 38.17 to 38.24), respectively. The above-mentioned S-Pb isotopic compositions indicate that the metallic materials involved in ore formation originated from a mixture of Triassic magmatic hydrothermal fluid and metamorphic basement. By integrating the regional geology, mineralization ages, and S-Pb isotopic studies, we propose that the Dongtangzi Zn-Pb deposit is the product of epigenetic hydrothermal fluid processes, driven by Late Triassic regional tectono-magmatic processes. Full article

Water electrolysis is a highly efficient route to produce ideally clean H₂ fuel with excellent energy conversion efficiency and high gravimetric energy density, without producing carbon traces, unlike steam methane reforming, and it resolves the issues of environmental contamination via replacing the conventional fossil fuel. Particular importance lies in the advancement of highly effective non-precious catalysts for the oxygen evolution reaction (OER). The electrocatalytic activity of an active catalyst mainly depends on the material conductivity, accessible catalytically active sites, and intrinsic OER reaction kinetics, which can be tuned via introducing N heteroatoms in the catalyst structure. Herein, the efficacious nitrogenation of CuS was accomplished, synthesized using a hydrothermal procedure, and characterized for its electrocatalytic activity towards OER. The nitrogen-doped CuO@CuS (N,CuO@CuS) electrocatalyst exhibited superior OER activity compared to pristine CuS (268 and 602 mV), achieving a low overpotential of 240 and 392 mV at a current density of 10 and 100 mA/cm², respectively, ascribed to the favorable electronic structural modification triggered by nitrogen incorporation. The N,CuO@CuS also exhibits excellent endurance under varied current rates and a static potential response over 25 h with stability measured at 10 and 100 mA/cm². Full article

With increasing concerns about global warming, the push for sustainable and eco-friendly fuels is accelerating. Propane, recognized as liquefied petroleum gas or LPG, has garnered research interest as an alternative fuel due to its notable advantages, including a high-octane rating, reduced greenhouse gas emissions, and potential cost-effectiveness. However, to realize its full potential as an alternative fuel it is essential to develop catalysts that efficiently handle emissions at low temperatures. In our research, we investigated three distinct palladium (Pd)-based three-way catalyst (TWC) formulations (PdRh, Pd-only, and Pd-OSC) to investigate the influence of typical TWC components rhodium (Rh) and oxygen storage components (OSC) in exhaust scenarios relevant to propane-fueled engines. Among these, the formulation containing oxygen storage components (Pd-OSC) showed the highest reactivity for both NO and C₃H₈ while minimizing performance degradation from hydrothermal aging (HTA). Notably, the temperature of 50% conversion (T₅₀) for propane in the Pd-OSC fresh and HTA sample was lower by 30 °C and 13 °C, respectively, compared to the Pd-only sample, highlighting the role of oxygen storage materials in enhancing catalyst performance, even without dithering. Additionally, N₂ physisorption showed that the Pd-OSC sample has a higher surface area and increased pore volume. This underscores the idea that OSC materials not only augment the catalyst’s porosity but also optimize reactant accessibility to active sites, thus elevating catalytic efficiency. In addition to evaluating performance, we further explored the performance and characteristics of the catalysts using catalytic probe reactions, such as water–gas shift and steam reforming reactions. Full article

To reduce air pollution worldwide, regulations on exhaust gas emissions from ships are becoming increasingly stringent. One fuel that is being considered as an alternative to replace the heavy fuel oil used in existing ship engines and thereby reduce harmful emissions, such as NO_x, SO_x, and greenhouse gases, is sulfur-free liquefied petroleum gas (LPG). To assess the viability of this alternative, it is necessary to understand propane reactivity, the main component of LPG, and develop after-treatment devices applicable to LPG engines. This research evaluated the performance of three prototype Pd-based three-way catalysts (TWCs) with varying Pd loadings (6.5, 4.1, and 1.4 g/L), focusing on their effectiveness concerning propane reactivity in LPG engines. For the fresh samples, catalysts with 4.1 g/L Pd demonstrated performance that was comparable to, or even surpassed, those containing 6.5 g/L Pd. Notably, the temperature of 50% conversion (T₅₀) for NO and C₃H₈ in the fresh Pd-4.1 was lower by 14 °C and 10 °C, respectively, compared to the fresh Pd-6.5 sample, despite having 37% less precious-metal loading. However, after hydrothermal aging at 900 °C for 100 h, the performance of the 4.1 g/L Pd catalyst significantly deteriorated, exhibiting lower efficiency than the 6.5 g/L Pd catalyst. The study also delved into various probe reactions, including the water–gas shift and propane steam reforming. Advanced analytical techniques, such as N₂ physisorption and scanning transmission electron microscopy, were employed to elucidate the texture and structural characteristics of the catalyst, providing a comprehensive understanding of its behavior and potential applications. Through this research, within the efforts of the maritime sector to address challenges posed by emission regulations and rising costs associated with precious metals, this study has the potential to contribute to the development of cost-effective emission control solutions. Full article

Hydrogen from biomass, as a promising alternative fuel, is becoming considerably attractive due to its high energy density and clean emissions. The aqueous phase reforming (APR) of biomass-derived oxygenated hydrocarbons and water is a renewable and efficient pathway for hydrogen production and shows great potential. However, the key to the application of this technique is to develop catalysts with high hydrogen productivity. In this work, we first synthesized polyaniline–platinum (PANI-Pt) organo-metallic hybrid precursors and then obtained a high-loaded (~32 wt.% Pt) and highly dispersed (~3 nm Pt particles) Pt@NC−400 catalyst after pyrolysis at 400 °C, and the nanoparticles were embedded in a nitrogen-doped carbon (NC) support. The Pt@NC−400 catalyst showed an almost three times higher hydrogen production rate (1013.4 μmol_H2/g_cat./s) than the commercial 20% Pt/C catalyst (357.3 μmol_H2/g_cat./s) for catalyzing methanol–water reforming at 210 °C. The hydrogen production rate of 1,2-propanediol APR even reached 1766.5 μmol_H2/g_cat./s over the Pt@NC−400 catalyst at 210 °C. In addition, Pt@NC−400 also exhibited better hydrothermal stability than 20% Pt/C. A series of characterizations, including ICP, XRD, TEM, SEM, XPS, N₂ physisorption, and CO chemisorption, were conducted to explore the physiochemical properties of these catalysts and found that Pt@NC−400, although with higher loading than 20% Pt/C (~23 wt.% Pt, ~4.5 nm Pt particle), possessed a smaller particle size, a more uniform particle distribution, a better pore structure, and more Pt metal active sites. This study provides a strategy for preparing high-loaded and highly dispersed nanoparticle catalysts with high hydrogen productivity and sheds light on the design of stable and efficient APR catalysts. Full article

The hydrothermal method is a frequently used approach for synthesizing HER electrocatalysts. However, a weak tolerance to high temperature is an intrinsic property of carbon cloth (CC) in most situations, and CC-based catalysts, which require complex technological processes in low-temperature environments, exhibit weak stability and electrochemical performance. Hence, we provide a new solution for these issues. In this work, MoO₃-NiS_x films of 9H5E-CC catalysts are synthesized, first through electrodeposition to form Ni particles on CC and then through a hydrothermal reaction to reform the reaction. The advantages of this synthetic process include mild reaction conditions and convenient operation. The obtained MoO₃-NiS_x film presents excellent catalytic activity and stability for HER. MoO₃-NiS_x film requires only a low overpotential of 142 mV to drive 10 mA cm⁻² for HER in 1.0 m KOH, and the obtained 9H5E-CF film only needs 294 mV to achieve 50 mA cm⁻² for OER. Remarkably, they also show excellent OER, HER, and full water splitting long-term electrochemical stability, maintaining their performance for at least 72 h. This work can be expanded to provide a new strategy for the fabrication of stable, high-performing electrodes using simple, mild reaction conditions. Full article