Search Results (205)

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

With the continuous consumption of fossil energy and the related environmental problems, clean energy, especially the hydrogen energy-derived water electrolysis, has attracted wide attention. However, as a result of the high energy consumption of water electrolysis and the limitations of single-function catalysts, there is an urgent need for cheap and simple-to-make bifunctional catalysts. In this work, based on the NiFe-LDH that is usually used for OER (Oxygen Evolution Reaction), doping of heteroatoms was carried out and a bifunctional catalyst could be then prepared using biomass as the carbon source. The preparation of catalyst precursors and in situ reduction were performed through the coupling process of hydrothermal and pyrolysis to enhance the electrolytic activity of the catalyst. Results showed that the overpotentials required to reach a current density of 10 mA·cm⁻² for the HER and OER processes were 305.2 mV and 310.4 mV, respectively, which are superior to the commercial catalysts. In the subsequent characterization, the structural characteristics of the catalyst support and their structure–activity correlation with active metals were systematically investigated by TEM, XRD, and XPS analysis, providing mechanistic insights into the catalytic behavior. The basic catalytic mechanisms of HER and OER were also obtained: the HER process was due to the formation of a Ni₃Fe alloy structure during catalyst preparation, which changed the electronic structure of the catalyst, while the OER process was induced by the formation of a NiOOH intermediate. The research results are expected to provide new ideas and data support for the preparation of bifunctional catalysts. Full article

Ammonia is increasingly recognised as a promising carbon-free fuel and hydrogen carrier due to its high hydrogen content, ease of liquefaction, and existing global infrastructure. However, its direct utilisation in combustion systems poses significant challenges, including low flame speed, high ignition temperature, and the formation of nitrogen oxides (NO_X). This review explores catalytic ammonia cracking as a viable method to enhance combustion through in situ hydrogen production. It evaluates traditional catalytic burner designs originally developed for hydrocarbon fuels and assesses their adaptability for ammonia-based applications. Special attention is given to ruthenium- and nickel-based catalysts supported on various oxides and nanostructured materials, evaluating their ammonia conversion efficiency, resistance to sintering, and thermal stability. The impact of the main operational parameters, including reaction temperature and gas hourly space velocity (GHSV), is also discussed. Strategies for combining partial ammonia cracking with stable combustion are studied, with practical issues such as catalyst degradation, NO_X regulation, and system scalability. The analysis highlights recent advancements in structural catalyst support, which have potential for industrial-scale application. This review aims to provide future development of low-emission, high-efficiency catalytic burner systems and advance ammonia’s role in next-generation hydrogen energy technologies. Full article

Ru/TiO₂ catalysts are well known for their high activity in the hydrogenation of CO₂ to CH₄ (the Sabatier reaction). This activity is commonly attributed to strong metal–support interactions (SMSIs), associated with reducible oxide layers partly covering the Ru-metal particles. Moreover, isothermal rates of formation of CH₄ can be significantly enhanced by the exposure of Ru/TiO₂ to light of UV/visible wavelengths, even at relatively low intensities. In this study, we confirm the significant enhancement in the rate of formation of methane in the conversion of CO₂, e.g., at 200 °C from ~1.2 mol g_Ru⁻¹·h⁻¹ to ~1.8 mol g_Ru⁻¹·h⁻¹ by UV/Vis illumination of a hydrogen-treated Ru/TiO_x catalyst. The activation energy does not change upon illumination—the rate enhancement coincides with a temperature increase of approximately 10 °C in steady state (flow) conditions. In-situ DRIFT experiments, performed in batch mode, demonstrate that the Ru–CO absorption frequency is shifted and the intensity reduced by combined UV/Vis illumination in the temperature range of 200–350 °C, which is more significant than can be explained by temperature enhancement alone. Moreover, exposing the catalyst to either UV (predominantly exciting TiO₂) or visible illumination (exclusively exciting Ru) at small intensities leads to very similar effects on Ru–CO IR intensities, formed in situ by exposure to CO₂. This further confirms that the temperature increase is likely not the only explanation for the enhancement in the reaction rates. Rather, as corroborated by photophysical studies reported in the literature, we propose that illumination induces changes in the electron density of Ru partly covered by a thin layer of TiO_x, lowering the CO coverage, and thus enhancing the methane formation rate upon illumination. Full article

Renewable energy-driven water electrolysis is widely regarded as a pivotal approach for achieving carbon-free hydrogen production. The development of highly efficient electrocatalysts is crucial to advancing the efficiency and scalability of electrolytic water splitting. Recent advancements in characterization techniques have revealed that catalysts often undergo surface reconstruction during the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), leading to the formation of real active species. Understanding the surface reconstruction process through advanced characterization methods is essential for the rational design of high-performance catalysts. However, the surface reconstruction of catalysts is a highly complex phenomenon, and conventional ex situ characterization techniques often fall short of capturing the dynamic evolution of the catalyst surface. Consequently, in situ characterization methods have emerged as indispensable tools for elucidating the surface reconstruction process. This paper provides a detailed review of the process of surface reconstruction, the reasons behind it, and the in situ characterization methods, and finally discusses the challenges faced by the characterization methods for the reconstruction of water electrolysis catalysts in future development. Full article

The global emphasis on clean energy has increased interest in producing hydrogen from petroleum reservoirs through in situ combustion-based processes. While field practices have demonstrated the feasibility of co-producing hydrogen and oil, the question of which offers greater economic potential, oil, or hydrogen, remains central to ongoing discussions, especially as researchers explore ways to produce hydrogen exclusively from petroleum reservoirs. This study presents the first integrated techno-economic model comparing oil and hydrogen production under varying injection strategies, using CMG STARS for reservoir simulations and GoldSim for economic modeling. Key technical factors, including injection compositions, well configurations, reservoir heterogeneity, and formation damage (issues not addressed in previous studies), were analyzed for their impact on hydrogen yield and profitability. The results indicate that CO₂-enriched injection strategies enhance hydrogen production but are economically constrained by the high costs of CO₂ procurement and recycling. In contrast, air injection, although less efficient in hydrogen yield, provides a more cost-effective alternative. Despite the technological promise of hydrogen, oil revenue remains the dominant economic driver, with hydrogen co-production facing significant economic challenges unless supported by policy incentives or advancements in gas lifting, separation, and storage technologies. This study highlights the economic trade-offs and strategic considerations crucial for integrating hydrogen production into conventional petroleum extraction, offering valuable insights for optimizing hydrogen co-production in the context of a sustainable energy transition. Additionally, while the present work focuses on oil reservoirs, future research should extend the approach to natural gas and gas condensate reservoirs, which may offer more favorable conditions for hydrogen generation. Full article

Electrocatalytic nitrate reduction to ammonia (ENRA) presents a promising strategy for simultaneous environmental remediation and sustainable ammonia synthesis. In this work, a Cu–Co bimetallic catalyst supported on functionalized reduced graphene oxide (RGO) was systematically designed to achieve efficient and selective ammonia production. Surface oxygen functional groups on graphene oxide (GO) were optimized through alkaline hydrothermal treatments, enhancing the anchoring capacity for metal active sites. Characterization indicated the successful formation of uniform Cu–Co bimetallic heterointerfaces comprising metallic and oxide phases, which significantly improved catalyst stability and performance. Among the studied compositions, Cu₆Co₄/RGO exhibited superior catalytic activity, achieving a remarkable ammonia selectivity of 99.86% and a Faradaic efficiency of 96.54% at −0.6 V (vs. RHE). Long-term electrocatalysis demonstrated excellent durability, with over 90% Faradaic efficiency maintained for ammonia production after 20 h of operation. In situ FTIR analysis revealed that introducing Co effectively promoted water dissociation, facilitating hydrogen generation (*H) and accelerating the transformation of nitrate intermediates. This work offers valuable mechanistic insights and paves the way for the design of highly efficient bimetallic electrocatalysts for nitrate reduction and ammonia electrosynthesis. Full article

An electrochemical sensor was developed for the detection of hydrogen peroxide (H₂O₂) based on the in situ formation of a nickel hexacyanoferrate complex on the electrode surface. Screen-printed carbon electrodes were modified with nickel-doped carbon nanodots (Ni-CNDs), and a nickel hexacyanoferrate complex was electrogenerated over the nickel carbon nanodots. Ni-CNDs were synthetized “a la carte” in one step by including nickel (II) acetate as precursor and characterized using different techniques: transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy, atomic force microscopy (AFM), and infrared spectroscopy (FTIR). The electrocatalytic activity toward H₂O₂ reduction and the oxidation of the resulting modified electrodes was studied. The developed sensor had a strong electrocatalytic effect on the oxidation and reduction of H₂O₂, yielding detection limits of 3.22 and 0.49 μM, respectively. The H₂O₂ content of a tap water sample was determined, confirming the viability of the developed electrochemical sensor. Full article

Currently, the electrochemical reduction of carbon dioxide faces significant challenges, including poor selectivity for C₂ products and low conversion efficiency. An effective strategy for optimizing the reduction reaction pathway and enhancing catalytic performance involves manipulating highly unsaturated atomic sites on the catalyst’s surface, thereby increasing the number of active sites. In this study, we employed sodium dodecylbenzenesulfonate (SDBS) as a surfactant in the electrodeposition method to synthesize copper cubes encapsulated with an amorphous shell (100 nm–250 nm) containing numerous defect sites on its surface. The electrocatalytic CO₂ reduction reactions in an H-type reactor showed that, compared to ED-Cu synthesized without additives, AS (amorphous shell)-Cu-5 exhibited a Faradaic efficiency value for ethylene that was 1.7 times greater than that of ED-Cu while significantly decreasing the Faradaic efficiency of hydrogen production. In situ attenuated total reflectance surface-enhanced infrared spectroscopy (ATR-SEIRAS) revealed that introducing an amorphous shell and abundant defects altered both the intermediate species and reaction pathways on the AS-Cu-5 catalyst’s surface, favoring C₂H₄ formation. The density functional theory (DFT) calculations further confirmed that amorphous copper lowers the energy barrier required for C-C coupling, resulting in a marked enhancement in FE-C₂H₄. Therefore, additive-assisted electrodeposition presents a simple and rapid synthesis method for improving ethylene selectivity in copper catalysts. Full article

The urgent need for sustainable CO₂ conversion technologies has driven the development of advanced photocatalysts that harness solar energy. This study employs a CTAB-assisted solvothermal method to fabricate a Z-scheme heterojunction Fe-MOFs/V_O-Bi₂WO₆ (FM/V_O-BWO) for photocatalytic CO₂ reduction. Positron annihilation lifetime spectroscopy (PALS) was employed to confirm the existence of oxygen vacancies, while spherical aberration-corrected transmission electron microscope (STEM) characterization verified the successful construction of heterointerfaces. X-ray absorption fine structure (XAFS) spectra confirmed that the defect configuration and heterostructure changed the surface chemical valence state. The optimized 1.0FM/V_O-BWO composite demonstrated exceptional photocatalytic performance, achieving CO and CH₄ yields of 60.48 and 4.3 μmol/g, respectively, under visible-light 11.8- and 1.5-fold enhancements over pristine Bi₂WO₆. The enhanced performance is attributed to oxygen vacancy-induced active sites facilitating CO₂ adsorption/activation. In situ molecular spectroscopy confirmed the formation of critical CO₂-derived intermediates (COOH* and CHO*) through surface interactions involving four-coordinated and two-coordinated hydrogen-bonded water molecules. Furthermore, the accelerated interfacial charge transfer efficiency mediated by the Z-scheme heterojunction has been conclusively demonstrated. This work establishes a paradigm for defect-mediated heterojunction design, offering a sustainable route for solar fuel production. Full article

Aqueous gel-casting provides a cost-effective and scalable approach for synthesizing nano-spherical Co₃O₄ powders, enabling precise control over particle morphology. In this study, Co₃O₄ powders were prepared using this method and evaluated as a catalyst precursor for the hydrolysis of sodium borohydride (NaBH₄). The effects of the monomer (acrylamide, AM)-to-metal molar ratio and initiator content (ammonium persulphate, APS) on particle size and catalytic performance were systematically explored. X-ray diffraction (XRD) analysis confirmed the formation of the Co₃O₄ phase at 400 °C, while transmission electron microscopy (TEM) images revealed particle sizes ranging from 16 to 85 nm, with higher AM and APS concentrations promoting finer particles. The optimized catalyst achieved a high hydrogen generation rate (HGR) of 28.13 L min⁻¹·cat.⁻¹, demonstrating excellent catalytic activity. Moreover, in situ-formed cobalt boride, derived from Co₃O₄ calcined at 600 °C for 2 h, exhibited an activation energy of 51.81 kJ mol⁻¹, comparable to Ru-based catalysts. This study underscores the aqueous gel-casting technique as a promising strategy for synthesizing efficient and low-cost hydrogen generation catalysts, offering an alternative to noble metal-based materials. Full article

This study used in situ modulation excitation spectroscopy (MES) with varying frequencies in a single experiment to identify surface species during ethanol oxidation on Au/SiO₂, Au/TiO₂, Au/ZnO, and Au/SrTiO₃. Fixed-bed reactor (FBR) tests (1 kPa ethanol, 1.5 kPa O₂, 513 K) showed that Au/SiO₂ and Au/SrTiO₃ had higher ethanol conversions. Au/SiO₂ favored acetaldehyde, while Au/SrTiO₃ yielded more acetates (acetic acid and ethyl acetate). Operando modulation excitation (ME)–phase sensitive detection (PSD)–DRIFTS, with ethanol and oxygen modulation, identified surface ethanol, acetaldehyde, acetates, ethoxy, and hydroxyl species. Oxygen modulation showed charge transfer to supports in Au/TiO₂ and Au/ZnO. At the fundamental frequency (f₀ = 1/90 Hz), ME–PSD–DRIFTS showed minimal adsorbed ethanol on Au/SiO₂, indicating high ethanol conversion. Au/SrTiO₃ had higher acetaldehyde consumption, correlating with increased acetates, consistent with FBR results. ME–PSD–DRIFTS at lower frequencies (0.07f₀, 0.5 f₀) and higher harmonics (2f₀, 3f₀) showed rapid ethoxy formation/decomposition, and slower acetaldehyde reactions, confirming acetaldehyde as a primary product and acetates as secondary products. Oxygen modulation revealed rapid hydrogen spillover and hydroxyl changes. Overall, operando spectroscopy via mass spectrometry confirmed the FBR findings. Full article

Chemical recycling of plastic waste, especially polyolefins, into valuable liquid fuels is of considerable significance to address the serious issues raised by their threat on environmental and human health. Nevertheless, the construction of efficient and economically viable catalytic systems remains a significant hurdle. Herein, we developed an efficient bifunctional catalyst system comprising γ-Al₂O₃-supported ruthenium nanoparticles (Ru/γ-Al₂O₃) and β-zeolite for the conversion of polyolefins into gasoline-range hydrocarbons. A yield of C_5–12 paraffins up to 73.4% can be obtained with polyethene as the reactant at 250 °C in hydrogen. The Ru sites primarily activate the initial cleavage of C–H bonds of polymer towards the formation of olefin intermediates, which subsequently go through further cracking and isomerization over the acid sites in β-zeolite. Employing in situ infrared spectroscopy and probe–molecule model reactions, our investigation reveals that the optimized proportion and spatial distribution of the dual catalytic sites are pivotal in the tandem conversion process. This optimization synergistically regulates the cracking kinetics and accelerates intermediate transfer, thereby minimizing the production of side C_1–4 hydrocarbons resulting from over-cracking at the Ru sites and enhancing the yield of liquid fuels. This research contributes novel insights into catalyst design for the chemical upgrading of polyolefins into valuable chemicals, advancing the field of plastic waste recycling and sustainable chemical production. Full article

Accurately identifying local interactions such as hydrophilicity and hydrophobicity is of critical importance in regulating the functions of amphiphilic biomolecules, but in situ identification methods for such interactions are still lacking. This study proposes a probe based on carbonyl (C=O) stretching vibration to study the hydrophilic and hydrophobic interactions in amphiphilic alcohol–water systems. A combination of theoretical calculations and Raman spectroscopy experiments is employed to investigate the molecular interactions of ethyl acetate C=O in an ethanol aqueous solution, as well as the reasons behind the splitting of spectral peaks. The results indicate that the spectral peak splitting of the C=O stretching vibration is attributed to ethyl acetate existing in different hydrophilic and hydrophobic environments. Specifically, the two low-wavenumber components arise from the formation of double and single hydrogen bonds between C=O and water or ethanol, respectively, while the high-wavenumber component is attributed to the interaction between C=O and the hydrophobic alkyl group. These findings suggest that the C=O stretching vibration of esters is sensitive to the surrounding hydrophilic and hydrophobic environments, thereby indicating its potential as a useful probe for identifying hydrophilic and hydrophobic interactions. Full article

Selective catalytic reduction of NO_x with H₂ (H₂-SCR) is crucial for eliminating NO_x emissions from hydrogen internal combustion engines (H₂-ICE). Although 1 wt.% Pt/SSZ-13 (Pt/SZ) is a promising H₂-SCR catalyst, it faces challenges such as a narrow operating window and low N₂ selectivity. Herein, the effects of WO₃ on improving the H₂-SCR performance of Pt/SZ was investigated. Results showed that incorporating 5 wt.% WO₃ significantly widened the temperature window for 80% NO_x conversion and enhanced N₂ selectivity at 90–180 °C. Several characterizations revealed that electrons transfer from W to Pt, so more active Pt⁰ species were formed on 1 wt.% Pt-5 wt.% W/SZ (Pt-5W/SZ). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis indicated that more active monodentate nitrates, nitrites, and NH₄⁺ species were generated on Pt-5W/SZ, which are key intermediates for N₂ formation. Consequently, the temperature windows for NO_x conversion (over 80%) and N₂ selectivity (over 70%) were widened by 65 °C and 66 °C, respectively. This work provides insights into the developing H₂-SCR catalysts with broader operating windows and higher N₂ selectivity. Full article