Reduction In Activation Energy Research Articles

Zr-MOF/MXene composite for enhanced photothermal catalytic CO2 reduction in atmospheric and industrial flue gas streams

In this study, a novel composite was engineered by integrating Zr-MOF (NH2-UIO-66) with MXene layers through electrostatic self-assembly. Under simulated sunlight and at 80 °C, this composite material achieved nearly complete conversion of low-concentration atmospheric CO2 to CO and CH4 without additional sacrificial agents or alkaline absorption liquids, marking one of the few reports demonstrating near-complete reduction of low-concentration CO2 directly from the air. For high-concentration CO2 in industrial flue gas, the composite utilized residual heat at 80 °C without additional energy input, exhibiting excellent CO2 reduction efficiency with CO and CH4 production rates of 127 μmol·g-1·h-1 and 330 μmol·g-1·h-1, respectively, resulting in a total production rate 4.76 times higher than that in the air. Compared to most reports on thermocatalytic CO2 reduction (>300 °C), this material shows significant advantages below 100 °C. The performance improvement is attributed to the introduction of Zr-MOF, which provides additional active sites and reduces activation energy. Additionally, the localized surface plasmon resonance (LSPR) effect of MXene facilitates the migration of thermal charge carriers to Zr4+ sites within the MOF. Density Functional Theory (DFT) calculations validate these findings. Overall, Zr-MOF/MXene composite holds potential for reducing CO2 in air and industrial settings, advancing energy conversion and environmental management.

Co-pyrolysis behaviors, kinetics, and thermodynamics of sludge, lignite and biomass through fixed-bed reactor experiments and thermogravimetric analysis

Co-pyrolysis behaviors, kinetics, and thermodynamic parameters of petrochemical sludge (PS), lignite (HL), and pine wood (PW) were investigated via fixed-bed reactor experiments and thermogravimetric analysis. Fixed-bed experiments showed H2 and CO2 were main gases from PS, HL, and blends, CO from PW and PS, and CO and CH4 from PS and HL. Thermal analysis indicated that ternary blends’ de-volatilization had two parts dominated by PW and HL, respectively. The comprehensive de-volatilization index increased from 7.0 × 10-7 to 3.3 × 10-6 %2/(min2·°C3) as PW ratio rose from 20 % to 40 %. Effects of heating rates on pyrolysis properties, kinetics, and thermodynamics were studied using thermal analysis data. Characteristic indices increased, and activation energies decreased with HL or PW mixing; minimum activation energy was 147.2 kJ/mol for PS and HL blend. Blending lignite and biomass improved pyrolysis indices of petrochemical sludge and reduced activation energy and thermodynamic parameters, benefiting sludge disposal.

Superionic conducting vacancy-rich β-Li3N electrolyte for stable cycling of all-solid-state lithium metal batteries.

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm-2) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li3N SSE. This vacancy-rich β-Li3N SSE shows a high ionic conductivity of 2.14 × 10-3 S cm-1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li3N achieve breakthroughs in high critical current densities up to 45 mA cm-2 and high capacities up to 7.5 mAh cm-2, and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li3N is unveiled as intrinsic stability to lithium metal. In addition, β-Li3N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li3N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi0.83Co0.11Mn0.06O2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g-1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g-1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li3N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm-2 for the compact pellet-type cells and around 2.2 mAh cm-2 for the all-solid-state lithium metal pouch cells.

Oxygen vacancy enriched and Cu single-atom contained covalent organic frameworks: A competitive photocatalyst to promote hydrogen evolution under visible light

Single-atom loaded covalent organic frameworks (COFs) have been rapidly developed in the field of photocatalytic hydrogen production in recent years. Despite the insufficient active sites has been introduced, the high recombination rate of photogenerated carriers has hindered the progress of catalyst development. In this work, a novel approach is proposed to construct oxygen vacancies (OVs) on single atom Cu contained COF-TpPa, acting as an electron collector to facilitate the transfer and utilization of electrons. The Cu-OV-TpPa can provide a remarkable H2 production rate of 2.77 mmol g−1 h−1 under visible light, which is 2.6 times of Cu-P-TpPa (a H2 production rate of 1.02 mmol g−1 h−1). It achieves a high apparent quantum efficiency (AQE) of 20 % at 420 nm with no noble metal cocatalyst. A thorough analysis of carrier lifetime, recombination rate, electric conductivity and charge density reveals that the synergistic effect between OVs and single-atom Cu significantly enhances photogenerated carrier separation efficiency and reduces activation energy. This study presents a new strategy to design COF-based photocatalysts towards a competitive H2 production under visible light.

Study of structural, elastic, optical, dielectric, and magnetic properties of sol-gel synthesized Li0.2Co0.3Zn0.3Fe2.2O4 ferrite for optoelectronic and electrical applications

This work presents a detailed investigation of the structural, elastic, optical, dielectric, and magnetic properties of Li0.2Co0.3Zn0.3Fe2.2O4 ferrite synthesized through the sol-gel process. The experimental structural parameters closely match the theoretical values, confirming the proposed cation distribution of the prepared sample. The FTIR spectrum and ultrasonic pulse transmission method analysis showed that the sample has brittle mechanical properties. According to UV-Vis optical absorbance analyses and based on Tauc's law, the sample exhibits a direct optical transition, with the band gap energy (Eg) determined to be 2.51 eV. The study of electrical conductivity showed that the sample exhibited a reduced activation energy (Ea= 0.154 eV) and remarkable electrical resistivity at room temperature (ρdc ∼ 104 Ω.m), indicating the material's potential for microwave device applications. The conduction process of the sample aligns with the NSPT model. Additionally, the temperature coefficient of resistance (TCR) suggests that the sample is a promising candidate for infrared radiation detection. A low coercive field was also derived from the hysteresis loop, confirming the soft nature of the sample operating within a microwave frequency range of 8–9 GHz. Our results show that the Li0.2Co0.3Zn0.3Fe2.2O4 compound offers advantages over the undoped Li0.5Fe2.5O4 compound, including a lower band gap, reduced activation energy, and higher electrical resistivity. This suggests that substituting Co and Zn into Li0.5Fe2.5O4 ferrites improves their performance in electrical and optoelectronic applications.

One‐step polymerization of polyvinyl alcohol/cashew gum/polypyrrole/copper oxide nanocomposites for high‐performance flexible films in optoelectronics

AbstractA ternary blend nanocomposite composed of polyvinyl alcohol/cashew gum/polypyrrole (PVA/CG/PPy) with varying contents of copper oxide (CuO) nanoparticles was synthesized via an in situ polymerization method, using water as an eco‐friendly solvent. Fourier‐transform infrared spectroscopy (FTIR), UV–visible spectroscopy, field emission scanning electron microscopy (FE‐SEM), x‐ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) were used to characterize the ternary blend nanocomposites. FTIR and UV–visible spectra demonstrated strong intermolecular interactions between the functional groups of the PVA/CG/PPy blend and the CuO nanoparticles. XRD patterns revealed that the CuO nanofillers were arranged in a structured manner within the ternary blend matrix. FE‐SEM confirmed the uniform dispersion and structured arrangement of CuO nanofillers at a concentration of 3 wt% within the blend matrix. TGA and DSC results showed that the addition of CuO nanoparticles to the PVA/CG/PPy blend improved both the thermal stability and glass transition temperature of the blend matrix. Electrical properties improved with CuO content up to 3 wt%, resulting in enhanced conductivity, an increased dielectric constant, and reduced activation energy. The highest tensile strength, 13.76 MPa, was also observed at this concentration. However, properties declined beyond 3 wt% due to agglomeration, making 3 wt% the ideal concentration for maximum performance. This study highlights the potential of PVA/CG/PPy/CuO nanocomposites for applications requiring improved electrical properties and thermal stability, particularly in flexible electronics and energy storage devices.Highlights Eco‐friendly synthesis of PVA/CG/PPy/CuO biopolymer nanocomposite films Improvement in morphological, and optical properties of PVA/CG/PPy/CuO films. CuO nanofillers magnify the thermal properties of the pristine PVA/CG/PPy Conductivity and dielectric characteristics: frequency and temperature dependence explored. PVA/CG/PPy/CuO nanocomposite films: pliable contenders unveiling industrial potentials.

Ultra-high energy storage efficiency achieved through the construction of interlocking microstructure and excitation of depressor effects

Glass-ceramic capacitors struggle to balance high energy storage efficiency (η>90 %) and sufficient breakdown field strength (Eb), hindering their use in energy storage. Interface polarization, caused by the accumulation of free charge, reduces breakdown strength. We prepared glass-ceramic materials with varying contents of the glass phase using traditional melting techniques, adjusting the glass content to enhance an interlocking structure between the glass and crystal phases, reducing Interface polarization. Divalent metal oxide BaO in the glass stimulated a depressor effect, filling gaps and increasing resistivity. The optimal composition (x = 0.2) achieved a 95 % energy storage efficiency and an energy storage density of 4.4 J/cm3 at 680 kV/cm, while x = 0.25 reached an ultra-high energy storage efficiency of 99 %. Increasing glass content reduced activation energy for Interface polarization (Ei) from 1.27 eV to 1.08 eV. Samples with x = 0.2 exhibited low dielectric loss (∼0.005), high dielectric constant (∼142), ultra-high power density (∼52.8 MW/cm3), and ultra-fast discharge speed (∼26 ns), suggesting future potential for high-performance glass-ceramic materials.

A comprehensive investigation of the impact of carbon-supported metal complexes of triaminoguanidine on the characteristics of a double-base propellant

ABSTRACT In this study, triaminoguanidine complexes grafted onto activated carbon (AC-TAG-Fe and AC-TAG-Co) were designed and investigated for their catalytic effect on the thermolysis of a double base propellant consisting of nitrocellulose (NC) and diethylene glycol dinitrate (DEGDN). The successful synthesis of transition metal complexes with triaminoguanidine and their subsequent grafting onto activated carbon were confirmed using various analytical techniques, including Fourier Transform Infrared Spectroscopy, Raman Spectroscopy, X-ray Diffraction, and Scanning Electron Microscopy. Thermal characterization using Thermogravimetric Analysis and Differential Scanning Calorimetry provided valuable insights into the thermal properties and reactivity of the elaborated NC/DEGDN-based composites. Importantly, the addition of various additives resulted in notable improvements in both the enthalpy of reaction and density. Isoconversional kinetic studies revealed that the incorporation of TAG-Fe and TAG-Co complexes reduced the apparent activation energy of the NC/DEGDN composite from 137.4 kJ/mol to 135.4 kJ/mol and 114.8 kJ/mol, respectively, suggesting their catalytic effect. Furthermore, it is found that the addition of activated carbon (AC) resulted in an increase in activation energy to 154 kJ/mol, whereas grafting TAG-Fe and TAG-Co complexes onto AC as a catalytic support subsequently reduced activation energy to 119 kJ/mol and 112 kJ/mol, respectively. Overall, this research serves as a valuable reference for future studies focusing on investigating the catalytic combustion characteristics of double-base solid propellants.

The Influence of Carbon Fiber on Crystallization and Morphology of Poly(Ether Ketone Ketone) Composites Towards High Rate Thermoplastic Manufacturing Processes

Recent interest in thermoplastic composites for aerospace applications is driven by the need for high-volume manufacturing of materials that display excellent mechanical, thermal, and solvent resistive properties. Specifically, a large component of the composite properties of thermoplastic composites are highly dependent on the crystalline fraction of the semi-crystalline polymer matrix of the reinforced system. This work investigates the melting behavior of poly (ether ketone ketone) (PEKK) and the influence of temperature and fiber on crystallization kinetics and morphology of (PEKK) composites utilizing, differential scanning calorimetry, Velaris-Sefaris modelling, and polarized optical microscopy (POM). Annealing temperatures of 380°C and above were required to fully erase crystalline ordering in the PEKK matrix. Furthermore, carbon fibers accelerated crystallization kinetics in PEKK at a range of temperatures observed via DSC, and Velaris-Sefaris modelling implied a shift from bulk to surface induced nucleation by the addition carbon fiber to the PEKK matrix, reducing activation energy of crystallization events. This nucleation behavior was visually confirmed through POM with observation of transcrystalline domains nucleated from the surface of a single carbon fiber.

The Influence of Carbon Fiber on Crystallization and Morphology of Poly(Ether Ketone Ketone) Composites Towards High Rate Thermoplastic Manufacturing Processes

Recent interest in thermoplastic composites for aerospace applications is driven by the need for high-volume manufacturing of materials that display excellent mechanical, thermal, and solvent resistive properties. Specifically, a large component of the composite properties of thermoplastic composites are highly dependent on the crystalline fraction of the semi-crystalline polymer matrix of the reinforced system. This work investigates the melting behavior of poly (ether ketone ketone) (PEKK) and the influence of temperature and fiber on crystallization kinetics and morphology of (PEKK) composites utilizing, differential scanning calorimetry, Velaris-Sefaris modelling, and polarized optical microscopy (POM). Annealing temperatures of 380°C and above were required to fully erase crystalline ordering in the PEKK matrix. Furthermore, carbon fibers accelerated crystallization kinetics in PEKK at a range of temperatures observed via DSC, and Velaris-Sefaris modelling implied a shift from bulk to surface induced nucleation by the addition carbon fiber to the PEKK matrix, reducing activation energy of crystallization events. This nucleation behavior was visually confirmed through POM with observation of transcrystalline domains nucleated from the surface of a single carbon fiber.

Improved ionic conductivity of La and Mg co-doped ceria nanocrystals synthesized by auto-combustion method

Ionic conductivity of La3+ and Mg2+ co-doped ceria, synthesized by auto-combustion method, is investigated here as electrolytes for intermediate-temperature solid oxide fuel cells (IT-SOFCs, operating below 800 °C). The prepared nanocrystalline electrolytes, LMDC10 (Ce0.9La0.05Mg0.05O2-δ) and LMDC20 (Ce0.8La0.1Mg0.1O2-δ) have exhibited improved ionic conductivities of 1.31 × 10−2 and 1.39 × 10−1 S cm−1 at 1073 K with reduced activation energies of 0.93 and 0.97 eV, respectively, when compared to conventional electrolytes like yttria-stabilized zirconia. The prepared samples are characterized by XRD, Raman spectra, XPS and FESEM which confirmed the formation of single-phasic cubic fluorite structure. Thus, the potential for La3+ and Mg2+ co-doped ceria electrolytes to offer cost-effective alternatives with low sintering temperatures and high performance for IT-SOFCs.

Synergistic effects of liquid phase sintering and B-site substitution to enhance proton conductivity of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ for protonic ceramic fuel cell

This paper is dedicated to improving the sintering and conductivity of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) by adding ZnO–CuO dual-sintering aids. The synergistic effects of liquid-sintering of Zn and B-site substitution of Cu on the sinterability and proton conductivity of BZCYYb are systematically investigated. X-ray diffraction (XRD) analysis of BZCYYb after addition of ZnO–CuO (BZCYYb-Zn-Cu) confirms the complete perovskite phase formation without any secondary phase. The substitution of Ce4+ (0.87 Å) with Zn2+ (0.74 Å) or Cu2+ (0.73 Å) induces a shift in XRD diffraction peak to higher angle due to a decrease in lattice constant. Energy dispersive X-ray spectroscopy analysis indicate a distinct distribution of Zn primarily at the grain boundaries, while Cu is predominantly located within the grains of BZCYYb-Zn-Cu. The addition of ZnO–CuO into BZCYYb results in a denser microstructure with larger average grain size. Furthermore, the substitution of Ce4+ by Cu2+ increases the concentration of oxygen vacancies and reduces activation energy. For BZCYYb-Zn-Cu, the proton conductivity reaches 4.52 × 10−2 S/cm at 750 °C, approximately 3 times higher than that of BZCYYb. This enhancement can be attributed to the synergistic effects of larger average grain size resulting from liquid phase sintering of Zn, low active energy, and high concentration of oxygen vacancies arising from Cu B-site substitution. BZCYYb-Zn-Cu is used as the electrolyte for anode support SOFC, and the single cell exhibits remarkable electrochemical performance and excellent stability in H2 fuel. This research establishes a crucial theoretical foundation for the preparation and performance evaluation for large-size protonic ceramic cell.

In-situ polymerized boehmite/ cashew gum/ polyvinyl alcohol/ polypyrrole blend nanocomposites with tunable structural, electrical, and mechanical properties for enhanced energy storage applications

This study describes the successful synthesis of boehmite (BHM) nanofiller-reinforced ternary blend nanocomposite films composed of polyvinyl alcohol (PVA), cashew gum (CG), and polypyrrole (PPy) using in-situ polymerization with water as the environmentally friendly solvent. The blend nanocomposites were characterized using Fourier-transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). FTIR analysis revealed chemical bonding between BHM and the biopolymer matrix at1071 cm-1. FE-SEM images exhibited a uniform distribution of BHM nanofillers within the CG/PVA/PPy matrix, particularly at a 10 wt% concentration. The addition of BHM significantly enhanced the thermal stability and the glass transition temperature of the nanocomposites. The temperature-sensitive AC conductivity, activation energy, and dielectric properties were examined using an impedance analyzer. AC conductivity analysis revealed reduced activation energy (1.277 × 10⁻5 eV at 7 wt% BHM) and increased dielectric constant (from 565.28 to 4411.22). The ternary blend nanocomposite demonstrated a significant 60.2 % increase in tensile strength, reflecting enhanced force resistance, while hardness values ranged from 26 to 30, classifying the films as soft and flexible. Overall, the study highlights significant enhancements in the morphological, electrical, thermal, dielectric, and mechanical properties of the nanocomposite films, emphasizing their promising potential for energy storage applications.

The universal gaseous detonation dynamics

The present communication proposes a new scaling approach to unify the dynamics of gaseous detonations subject to wall losses in both the narrow channels and small tubes, by compiling the published experimental data of detonations in 23 different mixtures with a very large range of cellular instabilities. A kinetic induction length Δi,loss can be determined from the detonation velocity deficit and detailed chemistry. In order to take into account the sensitivity of the latter length to post-shock temperature fluctuations (through the reduced activation energy θ), which is a partial and indirect marker of the cellular structure, and to bring out energetics (through the Chapman–Jouguet detonation Mach number MCJ), an effective kinetic length of Δi,loss(MCJ4/θ3) was built and has been shown to collapse the different detonation dynamics of various gaseous mixtures, subjected to wall losses, into a single universal curve for detonation velocity deficits.Novelty and Significance: Scaling analysis of large sets of published data of gaseous detonation experiments in narrow channels and small tubes has been made for 23 different mixtures with varied cellular instabilities and activation energies. The universal dynamics of gaseous detonations subject to wall losses in different mixtures has been achieved, for the first time, by adopting an effective kinetic length by taking into account the effect of both the activation energy and the energetics.

Phonon-Lithium Ion Interactions: A Case Study of LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La).

Li ion diffusion is fundamentally a thermally activated ion hopping process. Recently, soft lattice, anharmonic phonon, and paddlewheel mechanism have been proposed to potentially benefit the ion transport, while the understanding of vibrational couplings of mobile ions and anions is still very limited but essential. Herein, we accessed the ionic conductivity, stability, and especially, lattice dynamics in LiM(SeO3)2 (M = Al, Ga, In, Sc, Y, and La) with two different types of oxygen anions within a LiO4 polyhedron, namely, edge-shared and corner-shared with MO6 polyhedra, the prototype of which, LiGa(SeO3)2, has been theoretically reported before with the similar structural features to NASICON and later experimentally synthesized with the room temperature conductivity ∼0.11 mS cm-1. It is interesting to note that LiM(SeO3)2 with a higher Li phonon band center shows higher Li conductivity, which is in contradiction to the conventional understanding of the importance for soft lattice to superionic conductors. The anharmonic and harmonic phonon interactions as well as the couplings between the vibration of the edge-bonded or corner-bonded anion in Li polyanions and the Li ion diffusion have been studied in detail. With transition metal M changing from La, Y, In, Ga, Al, and Sc, anharmonic phonons increase with reduced activation energy for Li diffusion. The phonon modes dominated by the edge-bonded oxygen anions contribute more to the migration of the Li ion than those dominated by the corner-bonded oxygen anions because of the greater atomic interaction between the Li ion and the edge-bonded anions. Thus, rather than the overall lattice softness, attention shall be given to reduce the frequency of the critical phonons contributing to Li ion diffusion as well as to increase the anharmonicity, i.e., through asymmetric Li polyhedra, for the design of Li ion superionic conductors for all-solid-state batteries.

Enhanced photocatalytic hydrogen evolution by S-scheme heterojunction and metal phosphide in NiTiO3/Graphdiyne

A key strategy to improve photocatalytic reaction efficiency is to achieve effective separation and migration of photo-generated carriers. Heterojunctions and co-catalysts are essential for boosting charge separation and transfer, reducing activation energy, and providing active sites for surface redox reactions. Herein, we introduce a composite catalytic system based on NiTiO3, enhanced with Graphdiyne (GDY) and NiP, achieving a hydrogen production activity of 8.37 mmol g−1 h−1. This performance is attributed to the combined effects of S-scheme heterojunction formation and NiP nanoparticle generation through phosphorylation. The S-scheme heterojunction effectively separates electron-hole pairs, reducing charge transport distance. Additionally, NiP nanoparticles formed in situ promote faster charge separation from NiTiO3 and act as active sites to accelerate the reduction half-reaction. Consequently, NiTiO3/GDY-P exhibits higher light absorption, faster charge separation, and superior redox capacity compared to NiTiO3. This work presents an efficient, eco-friendly multiphase catalytic system based on an S-scheme heterojunction and metal phosphide.

Structural defect and activated alumina of spheric α-Al2O3 improving alumina ceramics density from the industrial coarse gibbsite

The quality of alumina ceramics generally depends on alumina powder. High-density alumina ceramics were prepared from industrial coarse gibbsite. Near-spheric α-Al2O3 with particles smaller than 500 nm was produced via the synergy of B and F from NH4BF4. The near-spheric α-Al2O3 calcined at low temperature generated alumina ceramics with high density and low porosity. Meanwhile, the wet pretreatment yielded smaller particles with structural distortion and high microstrain and aluminum hydroxide, notably increasing the relative density of alumina ceramics. 99.18% relative density, 0.017% porosity, and 27.54 GPa Vickers hardness of alumina ceramics were achieved at 1650°C for 2 h without additives and pressed sintering. In addition, the early stage of sintering of alumina green body followed particle boundary diffusion with reduced activation energy in the sintering process. The close packing of the spheric α-Al2O3, high microstrain of α-Al2O3, structural defects with considerable AlO4 units calcined at low temperature, structural distortion in the alumina, and activated alumina on the α-Al2O3 surface collectively promoted the densification of alumina ceramics, achieving remarkable hardness, high density, and tiny porosity.

Debromination of Pyrolytic oil from waste printed circuit boards by catalytic thermo chemical reactions with Ca(OH)2 and ZSM-5

The surge in Waste Electrical and Electronic Equipment (WEEE) volume presents a formidable disposal challenge. This study focused on catalytic pyrolysis of waste printed circuit boards (WPCBs) employing Ca(OH)2 alone and in conjunction with ZSM-5 as catalysts. Kinetic parameters for catalytic and non-catalytic pyrolysis were derived through thermogravimetric analysis (TGA). The Coats-Redfern method for non-catalytic pyrolysis showcased activation energies of 33.52, 405.81, and 67.96 kJ/mol in zones 1, 2, and 3, respectively with corresponding reaction orders of 0.9, 2.8, and 1.2. Introduction of Ca(OH)2 amplified activation energy and reaction order in zones 2 and 3. Subsequent incorporation of ZSM-5 with Ca(OH)2 resulted in reduced activation energy and reaction order in zone 2, while elevating them in zones 1 and 3. Validation through laboratory-scale fixed-bed reactor experiments confirmed TGA findings and unveiled that pyrolysis oil had enhanced phenolic yield because of ZSM-5 where Ca(OH)2 showcased its effectiveness in eliminating halogens.

Simultaneously Boosting Direct and Indirect Urea Oxidation of Nickel Hydroxide via Strategic Yttrium Doping.

Urea electrolysis can address pressing environmental concerns caused by urea-containing wastewater while realizing energy-saving hydrogen production. Highly efficient and affordable electrocatalysts are indispensable for realizing the great potential of this emerging technology. Among the numerous candidates, α-Ni(OH)2 has the merits of good electrocatalytic activity, adjustable heteroelement doping, and low cost; consequently, it has received tremendous attention in the electrolytic fields. Herein, a Y3+-doping strategy is developed to effectively enhance the catalytic performance of nickel hydroxide in the urea oxidation reaction (UOR). Our results show that Y3+ incorporation successfully modulates the electronic structure of α-Ni(OH)2 by inducing Ni3+ formation in the crystal lattice to initiate direct UOR, facilitates the Ni3+/Ni2+ redox transition with higher current responses to promote indirect UOR, and maintains the structural stability of YNi-10 (Ni2+/Y3+ molar ratio = 1:0.1) during long-term UOR operation. Owing to these features, the obtained YNi-10 sample exhibits a higher current density (127 vs 79 mA cm-2 at 1.5 V), a lower Tafel slope (48 vs 75 mV dec-1), a larger potential difference between the UOR and oxygen evolution reaction (OER, 0.26 vs 0.22 V at 80 mA cm-2), a higher reaction rate constant (1.1 × 105 vs 3.1 × 103 cm3 mol-1 s-1), and a reduced activation energy of UOR (2.9 vs 14.8 kJ mol-1) compared with the Y-free counterpart (YNi-0). This study presents a promising strategy to simultaneously boost direct and indirect UORs, providing new insights for further developing high-performance electrocatalysts.

Unlocking Fast Ionic Transport in Sub‐Nano Channels of MOF‐Based Electrolytes for Next‐Generation Batteries

AbstractIncorporating appropriate molecules into ordered porous framework materials plays a pivotal role in modulating their physicochemical properties and dynamic behaviors. Such frameworked materials are also applicable for the preparation of solid‐state electrolyte (SSE) with altered electrochemical performance. In this work, MOF (Metal‐Organic Framework)‐based frameworked electrolytes (FEs) are prepared by the introduction of conductive ion‐molecule complexes and have investigated the electrochemical behaviors. The angstrom‐level pores in the framework enable efficient interactions with the complexes and participation in ion transportation by altering the coordinating environments of Li+ ions. As a result, the activated MOF‐based SSE exhibits an impressive ionic conductivity of 4.0×10−4 S cm−1 at room temperature (RT), along with a notably reduced activation energy of 0.12 eV at 350 K. The MOF‐based FE has been applied to Li /FE /LiFePO4 batteries, which exhibit excellent long‐cycling performance with virtually no capacity loss over 1000 cycles at the current density of 2 C at RT. The novel Li+ transport mechanisms where ion‐molecules would actively participate in the interactions between the framework and Li+ ions, not only present a new strategy for enhancing the ion transport kinetics, but also deliver outstanding electrochemical performance promising for next‐generation batteries.