Search Results (132)

The imperative to mitigate climate change has accelerated the development of Carbon Capture, Utilization, and Storage (CCUS) technologies, particularly CO₂ hydrogenation into high-value chemicals and alternative fuels. This work evaluates the fundamental thermodynamic limitations and the primary directions of CO₂ conversion, with a primary focus on methanation, alongside related pathways such as methanol synthesis and the reverse water-gas shift (RWGS) reaction. To overcome the high kinetic barriers of CO₂ activation, various catalytic systems are analyzed. While noble metal catalysts exhibit high catalytic performance, nickel-based catalysts serve as a viable and cost-effective alternative. To overcome nickel’s susceptibility to thermal sintering and coking, advanced bimetallic and multimetallic formulations are being developed to enhance structural stability and selectivity. These advancements are crucial for producing Synthetic Natural Gas (SNG) and sustainable aviation fuels (SAF). Ultimately, the objective of this comprehensive review is to systematically summarize recent advancements in catalyst design, critically analyze the advantages and fundamental bottlenecks of distinct catalytic systems, and outline prospective paths for the efficient industrial-scale production of sustainable alternative fuels. Full article

The reverse water–gas shift (RWGS) reaction is a promising route for converting CO₂ into CO, an important feedstock for synthetic fuels and chemicals. In this study, Zn–Co zeolitic imidazolate frameworks (ZIFs), including ZIF-8, ZIF-67, ZIF-67-8, and the core–shell structures ZIF-8@67 and ZIF-67@8, were synthesized as catalyst precursors and thermally activated prior to catalytic testing. Transmission electron microscopy and elemental mapping confirmed the formation of well-defined core–shell architectures, while synchrotron X-ray diffraction verified the characteristic sodalite-type framework. Thermogravimetric analysis revealed substantial framework decomposition during activation at 700 °C. In situ time-resolved X-ray absorption spectroscopy (TR-XAS) showed that Zn remained predominantly in the Zn²⁺ state throughout heating, whereas Co²⁺ underwent progressive reduction to metallic Co⁰ at temperatures approaching 600 °C. Ex situ X-ray absorption spectroscopy confirmed the presence of Zn²⁺ species and metallic cobalt after activation. Catalytic testing of the activated ZIF-derived materials showed that Co-containing catalysts exhibited significantly higher RWGS activity than Zn-only ZIF-8-derived catalyst. Among the investigated samples, ZIF-67@8_C-500 achieved the highest performance, producing 2.50 μmol CO (equivalent to 50 μmol g⁻¹ catalyst) at 600 °C with a H₂/CO₂ ratio of 2:1. The strong dependence of activity on ZIF-67 core loading indicates that metallic cobalt generated from the Co-rich core plays a dominant role in CO₂ conversion. Thermal activation transformed the highly porous ZIF precursors into metallic Co-containing carbonaceous catalysts. The resulting structural evolution, rather than retention of the original porous MOF framework, governed the catalytic performance in the RWGS reaction. Full article

This study presents a comprehensive thermodynamic evaluation of several CO₂ conversion pathways, both non-catalytic and catalyst-assisted, using density functional theory (DFT) calculations in Gaussian 16 (B3LYP/6-311++G(d,p)). In the non-catalyzed section, three key routes are examined: hydrogenation (CO₂ + H₂ → CO + H₂O), dry methane reforming, and the reverse water–gas shift (RWGS). For the hydrogenation reaction, the Gibbs free energy change (ΔG) decreases from +0.018 to +0.005 Hartree as the temperature increases from 298.15 K to 1173.15 K, indicating a slight improvement in feasibility but still a high activation barrier of 0.326 Hartree, underscoring the need for catalysis. Dry methane reforming is both exothermic and spontaneous, with ΔG ≈ = −0.049 Hartree at 298.15 K and −0.030 Hartree at 593.15 K; however, operating under harsh conditions may accelerate degradation of reactor materials. In the catalyst-assisted section, copper surfaces and Cu₃M clusters (M = Sc, V, Ni, Cu, Co and Fe) are evaluated alongside two bimetallic catalysts, Fe₂ and Ni₂, under electrochemical CO₂ reduction (eCO₂RR) conditions. Scandium- and vanadium-doped clusters exhibit significant CO₂ adsorption, as evidenced by shifted vibrational frequencies between 800 and 1800 cm⁻¹ that signal C=O bond weakening. Under the evaluated thermobarometric conditions, Ni₂-containing systems displayed lower Gibbs energy values within their own optimized intermediate set and higher entropy values than the corresponding Fe₂-containing set, suggesting greater configurational flexibility and favorable stabilization trends. However, because Fe₂ and Ni₂ systems are chemically different, absolute total energies were not used as a standalone criterion for intrinsic catalytic superiority. Overall, while some non-catalytic routes become thermodynamically more favorable only at high temperature, the explicit inclusion of catalytic models, particularly doped Cu₃M clusters and Ni-containing systems, indicates enhanced CO₂ activation through stronger catalyst–adsorbate interactions, vibrational weakening of C=O bonds, and favorable electronic descriptors. These results suggest that catalytic systems may enable CO₂ conversion under milder conditions, although full kinetic confirmation requires comparative transition state calculations for each elementary catalytic step. Full article

Despite the fact that oxygen plasma treatments are widely used to modify the surface properties of polytetrafluoroethylene (PTFE), the long-term stability of these surface modifications has not been fully investigated. Specifically, the roles of morphological restructuring and chemical modifications at the surface remain to be understood. In this work, we treat commercial PTFE samples using O₂ plasmas at different discharge pressures to investigate their surface modifications and subsequent ageing at atmospheric pressure. We provide direct evidence that ageing behavior is governed by nanoscale and microscale restructuring of the plasma-modified interface, revealing a novel link between morphology dynamics and wettability properties. To capture this surface evolution, the modified interface was characterized using water contact angle (WCA) measurements, scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, and mass spectrometry (MS). Initial plasma treatment enhances PTFE hydrophobicity, shifting the WCA from ${\theta }_c\simeq 105°$ to a highly hydrophobic state of ${\theta }_c\simeq 135°$. By monitoring the samples in contact with air over a 67-day period a gradual transition toward hydrophilicity was revealed, with WCAs stabilizing at ${\theta }_c\simeq 70°$ after approximately 20 days. SEM observations identified time-dependent morphological degradation of plasma-induced nanostructures, while qualitative and quantitative FTIR analysis—utilizing the Specified Area Under Band (SAUB) method—confirmed corresponding shifts in carbonyl and hydrocarbon indices. These results demonstrate that ageing kinetics are a direct function of plasma pressure. The transition is further supported by a phenomenological fractal model, which confirms a morphological shift from an initial fractal surface ($d_s\simeq 2.25$) toward a standard flat geometry ($d_s=2$). Furthermore, calculations indicate a sign reversal in solid-gas interface tension parameters, reflecting the changed chemical nature of the surface. We conclude that the loss of hydrophobicity is driven by a synergistic interplay between morphological relaxation and chemical restructuring. Full article

This study investigates the synthesis of La_0.6Ca_0.4FeO₃ (LCF) perovskite via a ball milling method for application in reverse water–gas shift chemical looping (RWGS-CL) for CO₂-to-CO conversion. Unlike conventional wet-chemical routes such as the Pechini method, the ball milling approach offers a solvent-free, scalable synthesis using low-cost metal oxide precursors (e.g., La₂O₃, CaO, Fe₂O₃). Structural analysis by XRD confirmed the successful formation of single-phase cubic perovskite, with no secondary phases when using oxide precursors. Crystallite size increased with calcination temperature, from 118.9 Å (no calcination) to 404.3 Å (1050 °C). BET analysis revealed a decrease in surface area from 2.5 m²/g (no calcination) to 0.51 m²/g (1050 °C), consistent with sintering at higher temperatures. TPR-H₂ and TPO-CO₂ studies revealed that non-calcined LCF possesses slightly enhanced redox properties, with oxygen vacancy formation and CO₂ reoxidation activity both at 500 °C. RWGS-CL experiments demonstrate that all LCF samples exhibit stable CO production (910–970 µmol/g_LCF) over multiple cycles at 500 °C, with comparable performance across calcination conditions. A cost and sensitivity analysis reveals that the ball milling method had lower synthesis costs by approximately 92% at the laboratory-scale and 88% at the industrial-scale compared to the Pechini method, highlighting its strong potential for large-scale perovskite production. Full article

Oxygen vacancies are a key factor determining the efficiency of the CO₂ hydrogenation reaction and play a crucial role in CO₂ adsorption and activation. However, effectively regulating the concentration of oxygen vacancies to enhance the performance of the light-driven reverse water gas shift (RWGS) reaction remains a challenge. To address this, this study successfully developed Pt/TiO₂ catalysts with varying oxygen vacancy concentrations by controlling the morphology of TiO₂. Structural characterization results indicate that, compared to Pt/TiO₂-NR, Pt/TiO₂-NB exhibits a higher oxygen vacancy (O_V) concentration and greater CO₂ absorption. Catalytic performance evaluation results showed that under an irradiance of 2.5 W/cm², the CO production rates of the Pt/TiO₂-NB catalyst reached 57.03 mol·g_Pt⁻¹·h⁻¹. Furthermore, the catalyst maintained excellent catalytic stability during 45 h of continuous operation, demonstrating good potential for practical applications. Full article

Given the critical need for scalable technologies that decouple industrial production from fossil feedstocks, this study introduces a green hydrogen-driven and carbon-negative industrial complex that employs renewable energy to simultaneously produce methanol and Fischer–Tropsch hydrocarbon products via feedstocks of carbon dioxide (CO₂) and water. The proposed complex (FARMOW) integrates six major sections: (i) a Fischer–Tropsch synthesis process (FTSP), (ii) an alkaline water electrolysis process (AWEP), (iii) a reverse water–gas shift process (RWGSP), (iv) a methanol synthesis process (MSP), (v) an off-gas combustion process (OGCP), and (vi) a water treatment process (WTP). In this complex, the green hydrogen produced from AWEP is reacted with CO₂ from a carbon capture unit and sent to the MSP and FTSP sections, respectively, to generate methanol and Fischer–Tropsch hydrocarbon products. The byproduct (water) from the complex is utilized to generate steam through rigorous process simulation, and the technical efficacy of the complex has been modeled and validated, yielding high-value hydrocarbons, methanol, steam, and oxygen. Furthermore, a comprehensive techno-economic assessment with sensitivity analysis is performed to evaluate the commercial flexibility of the system under varying market conditions. Full article

Amid growing pressure to reduce carbon emissions, carbon capture, utilization, and storage (CCUS) has become an important pathway toward deep decarbonization. However, the conventional separated “capture–release–conversion” process suffers from high energy consumption and system complexity, which severely limits its large-scale application. Integrated CO₂ Capture and Utilization (ICCU), which enables the capture, activation, and conversion of CO₂ within a single system, has attracted widespread attention because it can effectively reduce intermediate energy-intensive steps and improve carbon utilization efficiency. This review systematically summarizes recent progress in ICCU technology, with particular emphasis on reaction mechanisms and interfacial coupling characteristics. The performance features of solvent-based chemical absorption and solid-sorbent adsorption, two widely studied capture routes, are summarized, and typical integrated conversion pathways, including reverse water–gas shift, methanation, and dry reforming of methane, are discussed. On this basis, the roles of non-conventional energy-assisted strategies, such as photocatalysis, electrocatalysis, non-thermal plasma, and microwave irradiation, in expanding ICCU systems are further examined, together with their system-level coupling potential in carbon-intensive industries such as steel, cement, and power generation. Finally, the key scientific issues and engineering challenges currently facing ICCU are analyzed from the perspectives of fundamental mechanisms, material design, and system engineering, and future development directions are proposed. This review highlights that elucidating multiscale synergistic mechanisms, developing high-performance dual-function materials, and optimizing system integration are crucial to promoting the industrial application of ICCU technology. Full article

The efficient conversion of methane into hydrogen-rich syngas is essential for sustainable energy; however, integrating methane partial oxidation (POM) with the water–gas shift (WGS) reaction remains a significant challenge due to thermal and kinetic mismatches. This research presents a spatially decoupled dual-bed reactor configuration, utilizing Ni/GDC and Cu/GDC catalysts, to achieve synergistic hydrogen production. Unlike conventional physically mixed systems, which suffer from thermal hotspots and the unintended promotion of the endothermic Reverse Water–Gas Shift (RWGS) reaction, the dual-bed architecture effectively segregates the reaction zones. Advanced characterization, including O₂-TPO and Raman spectroscopy, reveals that the GDC support acts as a critical oxygen buffer via the Mars-van Krevelen mechanism, modulating the dynamic redox state of the active metal sites to prevent deep oxidation and carbonaceous deactivation. Furthermore, macroscopic performance and carbon–oxygen mass balance analyses confirm that this rational architectural design facilitates a seamless integration of POM and WGS pathways, resulting in significantly maximized H₂ yield. From a broader engineering perspective, this dual-bed strategy offers a practical, low-complexity alternative to intensive integrated technologies such as sorption-enhanced reforming (SER) or chemical looping, providing a robust and scalable framework for durable, high-efficiency hydrogen production. Full article

Dry reforming of methane (DRM) converts the greenhouse gases methane (CH₄) and carbon dioxide (CO₂) into syngas (hydrogen (H₂) and carbon monoxide (CO)). Despite its numerous advantages, DRM has not yet been industrialized due to catalyst deactivation and competing side reactions. While Ni-based catalysts have been widely used, they are prone to increased carbon deposition and sintering, and although bimetallic systems and oxygen-based supports have shown promise, their effects on carbon deposition are yet to be fully understood. In this study, carbon nanotube (CNT)-supported Pt-Ni catalysts incorporating mixed oxides of CeZrO₂ and CeZrLaO₂ were investigated to evaluate the impact of support composition and metal–support interactions in DRM. The catalysts were synthesized and subsequently tested in DRM. Catalysts supported on CNTs displayed higher CH₄ and CO₂ conversions compared to conventional ceria–zirconia, highlighting the beneficial role of the carbon nanotube support in improving dispersion and accessibility of the metal active sites. Addition of Pt was found to promote reverse water–gas shift (RWGS) reaction, whereas the addition of La was found to decrease catalytic activity. Despite the formation of a Ni-Pt alloy, the obtained catalysts favored RWGS over DRM. These findings illustrate key limitations and design considerations for optimization of CNT-supported bimetallic catalysts in DRM. Full article

As the global imperative for climate neutrality intensifies, hydrogen (H₂) from fossil fuels remains central to decarbonizing hard-to-abate sectors. Conventional production via steam methane reforming (SMR), however, is carbon-intensive and, even with carbon capture and storage (CCS), incurs energy penalties and long-term storage constraints. This review develops a harmonized well-to-gate, market-oriented framework to evaluate methane pyrolysis (MP) relative to SMR and autothermal reforming (ATR), with or without CCS, moving beyond reactor-focused assessments toward system-level commercialization analysis. MP decomposes methane into hydrogen and solid carbon, avoiding direct CO₂ formation and the need for CCS infrastructure. Integrating with the reverse water–gas shift (RWGS) reaction enables flexible syngas production with adjustable H₂:CO ratios for methanol and chemical synthesis. A central finding is the dominant role of the “carbon lever”: MP generates approximately 3 kg of solid carbon per kg of H₂, making the carbon market’s absorptive capacity the primary scalability constraint. While carbon monetization can reduce levelized hydrogen costs, large-scale deployment would rapidly saturate existing carbon black and specialty carbon markets. Techno-economic evidence indicates that carbon prices above $500/ton are required to achieve parity with gray hydrogen, whereas $150–200/ton enables competitiveness with blue hydrogen. Lifecycle assessments further show that climate superiority over SMR or ATR with CCS requires upstream methane leakage below 0.5% and very low-carbon electricity. Commercial readiness varies, with plasma MP at TRL 8–9 and thermal, catalytic, and molten-media pathways remaining at the pilot or demonstration stage. Parametric decision-space analysis under harmonized boundary assumptions shows that MP is not a universal substitute for reforming but a conditional pathway competitive only under aligned conditions of low-leakage gas supply, low-carbon electricity, credible carbon monetization, and supportive policy incentives. The review concludes with a roadmap that highlights standardized carbon certification, end-of-life accounting, and long-duration operational data as priorities for commercialization. Full article

CO₂-assisted catalytic pyrolysis presents a viable and promising approach to addressing plastic waste pollution and mitigating climate change. However, the effects of the metal–catalyst combination mode and the spatial distance between metal–acid sites on catalytic performance remain unclear. In this study, the reaction behaviors of the configurations, Fe₃O₄ and ZSM-5 in tandem catalysis (Fe₃O₄&HZ), their physical mixture (Fe₃O₄-HZ), and Fe-loaded ZSM-5 (Fe/HZ), were compared in polypropylene pyrolysis under a CO₂ atmosphere. The aromatic contents followed this order: Fe/HZ > Fe₃O₄-HZ > Fe₃O₄&HZ > ZSM-5 > Fe₃O₄. Specifically, Fe/HZ with the highest degree of metal–zeolite proximity achieved an aromatic content of 66.1%, significantly higher than the 34.2% obtained with Fe₃O₄&HZ, demonstrating that closer metal–acid proximity promoted aromatic formation. Moreover, Fe/HZ significantly reduced coke deposition. Based on characterization results from XRD, SEM, TEM, XPS, and NH₃-TPD, the enhanced spatial proximity between metal and acid sites strengthened the functional synergy between iron-based redox sites and zeolitic Brønsted acid sites. This synergy facilitated the reverse water–gas shift reaction of CO₂, which consumed hydrogen generated during aromatization and shifted the reaction equilibrium toward enhanced aromatic production. These findings would offer theoretical and strategic insights into the optimization of CO₂-assisted catalytic pyrolysis systems for the sustainable upcycling of plastic waste. Full article

In this work, a rational catalyst design based on interfacial architecture engineering is proposed for low-temperature dry methane reforming (DMR) at 550 °C. Ni-based catalysts containing 10 wt% Ni were developed on a γ-Al₂O₃ support modified with 9 wt% MgO–1 wt% ZrO₂. Zirconia promoters were introduced either by dry impregnation or via an ammonia vapor-assisted route to construct a Ni–NiO–ZrO₂ interfacial network. The effects of ZrO₂ content (0, 1, and 3 wt%) and synthesis route on metal–support interactions, oxygen mobility, and coke resistance were systematically investigated. ZrO₂ promotion increased the fraction of reducible Ni species and preferentially enhanced CO₂ activation, thereby promoting the reverse water–gas shift (RWGS) reaction and lowering the H₂/CO ratio. In contrast, ammonia vapor-assisted preparation induced the formation of an LDH-derived Ni–NiO–ZrO₂ surface network, which increased the concentration of surface-accessible Ni species, suppressed excessive zirconia coverage, and significantly improved apparent oxygen mobility. These synergistic structural features are consistent with enhanced oxygen-assisted carbon removal and improved coke management through regulation of the nature of carbon species, leading to more balanced activation of CH₄ and CO₂. Overall, this study provides insights into interfacial structure–performance relationships for designing efficient Ni-based catalysts for CO₂ utilization. Full article

Mo/ZZG and W/ZZG nanomaterials for the catalytic reduction of CO₂ were successfully prepared from preformed ZnO-ZrO₂-Ga₂O₃ (ZZG) and HPMo and HPMo heteropolyacids via simple incipient wetness impregnation. To establish the relationship between structural properties and catalytic performance, the prepared catalysts were deeply characterized using XRD, Raman spectroscopy, SEM coupled with EDX, BET, XPS, and H₂-TPR techniques. The catalytic performance of the materials was evaluated in the RWGS reaction under atmospheric pressure, using a feed composition of CO₂/H₂/N₂ = 1/3/1 across a temperature range of 250–600 °C. All materials were active in the reverse water gas shift reaction (RWGS) under these conditions, with the Mo/ZZG catalyst exhibiting the best performance, demonstrating excellent catalytic activity at low temperature with the lowest activation energy and the highest CO₂ to CO conversion efficiency. Full article

Propylene (C₃H₆) is a vital building block in the chemical industry as it serves as a key raw material for producing plastics, synthetic fibers and numerous daily-use chemicals. However, the current production routes of C₃H₆ are energy-intensive and face sustainability challenges, prompting the scientific community to explore alternative technologies for its production. The oxidative dehydrogenation of propane (ODHP) using CO₂ as a soft oxidant offers a safe and sustainable pathway for C₃H₆ production, where CO₂ can act as a hydrogen scavenger, coke suppressor and site re-activator. Gallium- and chromium-based catalysts are among the most studied systems for CO₂-assisted ODHP, yet they operate by distinct mechanisms: Ga catalysts follow pathways where both acidic and basic sites are involved, while Cr catalysts rely on redox cycles involving variations in the oxidation state of chromium. In addition to performance and reaction mechanism, Ga- and Cr-based catalysts differ markedly in terms of sustainability, with Cr systems facing environmental and regulatory challenges associated with Cr⁶⁺ species toxicity, while Ga systems, although less toxic, are constrained by gallium scarcity and cost. This review compares Ga- and Cr-based catalysts side by side, emphasizing how support effects, addition of promoters and mechanistic insights fine tune their performance. The aim is to highlight the advantages, the limitations as well as the sustainability implications of these materials and finally to outline future directions for designing more efficient and environmentally friendly catalysts for propylene production. Full article