Industrial Chemistry & Materials最新文献

Photoelectrocatalytic (PEC) hydrogen production represents a pivotal technology for sustainable energy conversion, yet its efficiency is fundamentally limited by rapid charge recombination and sluggish reaction kinetics. This review highlights internal electric field (IEF) engineering as an innovative strategy to overcome these challenges by rationally designing catalysts at the nanoscale. We systematically discussed how tailored IEFs construction via heterojunctions, doping, surface modification, and strain engineering can dramatically enhance charge separation, transport, and surface redox kinetics in photoelectrocatalysts. By elucidating the underlying mechanisms (e.g., band bending, dipole effects, and interfacial screening), we summarized universal principles for IEF manipulation across diverse materials, including metal oxides, chalcogenides, and 2D heterostructures. Furthermore, we critically evaluate performance breakthroughs in solar-to-hydrogen conversion enabled by IEF optimization. Challenges such as field stability under operational conditions and scalability are addressed, alongside emerging opportunities in machine learning aided design. This work not only provides a guide for next-generation photoelectrocatalysts but also extends IEF strategies to broader energy applications, underscoring their transformative potential in achieving carbon neutrality.

Keywords: Internal electric field; Hydrogen evolution reaction; Heterojunction; Surface modification.

Addressing the limitations of conventional organic polymer coatings in thermal management, this study developed an eco-friendly micro-3D expanded graphite powder (MEGP) protection coating that integrates exceptional heat conduction and heat radiation. In terms of thermal conductive filler selection, expanded graphite (EG) with a micro 3D structure was selected as the filler framework of the composite coating, and a self-assembled functional filler (MEG) was obtained after modification with an as-prepared corrosion inhibitor of a Schiff base–Ce complex (SP), which formed a 3D conductive network in the coating by electrostatic self-assembly. The unique architecture endowed MEGP with a remarkable thermal conductivity of 2.6 W m⁻¹ K⁻¹, 12-fold higher than that of pure epoxy (common resin for anti-corrosion coatings) and high infrared emissivity (0.95–0.98 at the full spectrum range of 2.5–25 μm), synergistically enhancing heat dissipation through dual conduction and radiation mechanisms. Finite element simulations confirmed superior thermal management performance. Simultaneously, the MEGP coating exhibited robust adhesion (10.4 MPa) and impact resistance (100 cm). Moreover, the impedance modulus of the coating at 0.01 Hz remains above 10⁸ Ohm cm² during 90 d immersion in a 3.5 wt% NaCl solution, benefiting from the Schiff base–Ce complex. The structure–property relationships between the 3D network architecture and multifunctional performance were elucidated by a systematic study. This novel design provides a new method for preparing functional integrated coatings with high thermal conductivity.

Keywords: Thermal conductivity; Infrared emissivity; Schiff base; Anti-corrosion; Powder coating.

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This review presents recent advances in coupling in situ hydrogen peroxide (H₂O₂) synthesis with selective oxidation reactions. As a green oxidant, H₂O₂ plays an important role in the chemical industry. However, conventional production methods often yield highly concentrated H₂O₂, which is not suitable for direct use in reactions and raises significant safety concerns. The integration of in situ H₂O₂ generation with selective oxidation allows for the immediate use of low-concentration H₂O₂, improving both safety and process efficiency. This review summarizes various strategies for in situ H₂O₂ production, including enzymatic and catalytic approaches, and discusses their application in representative oxidation reactions such as olefin epoxidation, benzene hydroxylation, methane oxidation, adipic acid synthesis, Fenton processes, oxidative desulfurization, and the oxidation of sulfides to sulfones. Special attention is given to recent developments in catalyst composition and structural design, particularly in olefin oxidation. This review concludes with a summary of the advantages of in situ H₂O₂ synthesis and offers perspectives on future research directions aimed at improving reaction efficiency, economic feasibility, and the development of sustainable green chemistry technologies.

Keywords: In situ hydrogen peroxide; Olefin epoxidation; Benzene hydroxylation; Tandem reaction; Desulfurization.

Electronic information materials (EIMs) are key enablers for building a smart society. As the material carriers of next-generation information technology, the development of EIMs is increasingly constrained by the challenges of manufacturing precision, heterogeneous integration reliability, and circular economy compatibility. As traditional approaches struggle to meet the demands for nanoscale machining, low power consumption, structural flexibility, and environmental compatibility, there is an urgent need for disruptive materials and methodologies. Ionic liquids (ILs), with their unique combination of tunable molecular structures, negligible volatility, broad electrochemical windows, and strong solvation capabilities, offer a promising route to address these bottlenecks. As dynamic reaction media, ILs precisely regulate the nucleation kinetics and interfacial behaviours of zero dimension (0D) quantum dots, one dimension (1D) nanowires, and two dimension (2D) semiconductors through their unique solvation environments, yielding advanced materials with next-generation EIMs. Leveraging hydrogen bonding and ion-exchange interactions, ILs enable selective extraction and recycling of critical electronic chemicals (e.g., rare earth elements, conductive polymers), offering greener alternatives to conventional solvent-based processes. In field-effect transistors and flexible electronics, ILs improve charge transport efficiency, reduce operating voltages, and enhance interfacial stability, while their compatibility with heterogeneous integration addresses reliability challenges in scalable manufacturing. This review systematically examines ILs roles in advancing EIMs and proposes design principles for their targeted application, highlighting their potential to drive sustainable innovation in electronic materials science.

Keywords: Ionic liquids; Electronic information materials; Separation and purification; Electronic devices.

Soft porous crystals (SPCs), particularly soft metal–organic frameworks (MOFs), represent a promising class of crystalline porous materials distinguished by their structural flexibility, dynamic behavior, and strong responsiveness to external stimuli. These features set them apart from conventional rigid materials and make them highly attractive for advanced technological applications. Despite extensive research on MOFs overall, soft MOFs remain relatively underexplored, and further investigation into their potential is essential for advancing materials science and enabling next-generation technologies. Although both SPCs and their rigid counterparts face common challenges in long-term operational stability (thermodynamic, chemical resistance, and mechanical durability) and large-scale high-quality production, the adaptive properties of SPCs—such as energy efficiency, high selectivity, and high capture efficiency—open up new frontiers for industrial production and real-world applications. In this perspective, to gain a comprehensive understanding of their promising applications, the research landscape is divided based on dosage usage regarding scaling softness, covering both (i) moderate and high-dose applications (storage and separation, catalysis, and energy storage) and (ii) trace or low-dose applications (electronic devices, biomedicine, and nuclear industry), and summarize the key technological fields within each category. It should be noted that high-quality SPCs can typically be obtained at low doses. However, at high doses, the increased presence of defects or disorder may lead to non-uniform structural transformations that propagate through the material. This behavior must be carefully considered in practical applications. Ultimately, an insightful outlook on the promising prospects of SPCs is provided.

Keywords: Soft porous crystals; Metal–organic frameworks; Flexibility; Applications; Industrialization.

Tin-oxo clusters (TOCs) are promising candidates for next-generation extreme ultraviolet (EUV) photoresist materials due to their strong EUV absorption properties and small molecular sizes. The surface ligands are critical to the photolithographic patterning process; however, the precise regulatory mechanisms governing their functionality require further investigation. Building upon our previously reported Sn4-oxo clusters, Sn4–Me–C10 and Sn4–Bu–C10, which incorporate butyl and methyl groups, respectively, this study presents the synthesis of a novel cluster, Sn4-MB, which integrates both butyl and methyl groups within the same Sn4-oxo core. This new compound demonstrates superior patterning performance compared to both Sn4–Me–C10 and Sn4–Bu–C10, as well as their mixed formulations. The enhanced performance is attributed to the intramolecular hybridization between Sn–methyl and Sn–butyl moieties in Sn4-MB, which facilitates radical feedback regulation, thereby minimizing energy dissipation and suppressing the extent of reaction diffusion during pattern formation. In electron beam lithography (EBL) exposure experiments, optimization of the developer and reduction of film thickness allowed Sn4-MB to achieve lines with a critical dimension (CD) of 17 nm. Furthermore, during EUV exposure, Sn4-MB produced 75 nm pitch lines at a dose of 150 mJ cm⁻², with a line CD of 33 nm. This study provides an effective molecular design strategy for enhancing the lithographic performance of TOC photoresists, highlighting their substantial potential for next-generation EUV lithography applications.

Keywords: Tin-oxo clusters; Intramolecular radical regulation; Photoresist; Electron beam lithography; Extreme ultraviolet lithography.

Integrated carbon capture and utilization (ICCU) has emerged as a promising strategy toward carbon neutrality. However, most existing studies rely on simulated flue gas compositions, neglecting the impact of common impurities such as sulfur oxides (SO_x) and nitrogen oxides (NO_x), thereby limiting the practical industrial applicability of ICCU technologies. Herein, we systematically investigate the effects of SO₂ and NO₂ at various concentrations on the adsorption–catalysis performance based on a representative Ni–Ca dual functional material (DFM) in the ICCU–dry reforming of methane (ICCU-DRM) process. Exposure to 100 ppm SO₂ showed a negligible influence on catalytic activity but markedly inhibited carbon deposition. Further increasing the SO₂ concentration to 500 ppm led to complete deactivation of the DFM. NO₂ exhibited a similar concentration-dependent trend to SO₂, albeit with a comparatively lower impact. Mechanistic analysis revealed that both SO₂ and NO₂ promote the formation of a coating layer of calcium-containing compounds on the surface of Ni nanoparticles, accounting for the partial or total deactivation. These findings offer critical insights into the industrial applications of ICCU systems under realistic flue gas conditions.

Keywords: Integrated carbon capture and utilization; SO_x and NO_x; Deactivation; Phase transition; DRM.

Hydrogen generation through conventional water electrolysis (CWE) is becoming increasingly prevalent on an industrial scale. However, widespread implementation is partially hampered by the sluggish kinetics of the oxygen evolution reaction (OER) and the severe (energy) costs associated with it. The electrooxidation of alcohols has received great interest within the scientific community as a potential alternative to the OER, leading to the emergence of a novel field known as hybrid water electrolysis (HWE). Nevertheless, while many efforts have been made by multiple stakeholders to give direction to CWE research with the aim of boosting its widespread industrial implementation, the same cannot be said for HWE. In this work, we provide an overview of target performance indicators for industrial alkaline CWE, and we discuss the extent to which the alcohol oxidation reaction (AOR), conducted under similar conditions, reaches those targets. Furthermore, we identify and discuss additional targets required for industrial application of HWE, with specific sections dedicated to the topics of selectivity and circularity of HWE products. In addition to this, we discuss the role that effective reactor design has in combating challenges associated with upscaling of HWE, followed by a description of novel approaches used in the literature. Finally, recommendations are given aiming to direct future research efforts towards industrial application of the AOR with simultaneous hydrogen production.

Keywords: Electrolysis; Alcohol electrooxidation; Alkaline water electrolysis; Hybrid water electrolysis; Industrially relevant conditions.

Separation of iso-butene and iso-butane is vital to producing high purity iso-butene feedstock, but is challenging because of their close molecular size and properties. Adsorptive separation using porous materials like metal organic frameworks (MOFs) is emerging as a potential energy-efficient alternative. But it's hindered by the lack of porous materials that exhibit satisfactory iso-butene/iso-butane separation performance. In this study, a novel sulfonate functionalized material, ZU-603, is reported to achieve the benchmark separation performance of iso-butene/iso-butane via exploiting the geometric difference of the carbon backbone between the planar iso-butene and tetrahedral iso-butane. Single-crystal analysis of ZU-603 loaded with iso-butene and simulation studies reveal that the sulfonate sites bound the iso-butene via S^δ−⋯H^δ+C interactions, meanwhile iso-butene molecules are efficiently stacked via π–π interactions within the confined space, realizing higher stacking efficiency of iso-butene than iso-butane. ZU-603 shows an exceptionally high iso-butene adsorption uptake of 2.30 mmol g⁻¹ (298 K, 1 bar) and a record high iso-butene/iso-butane uptake ratio of 2.77 at 1 bar, outperforming previously reported benchmarking materials (1.2). Fixed-bed breakthrough experiments confirm the impressive iso-butene/iso-butane dynamic separation ability of ZU-603. The work provides a potential shape-recognition strategy in designing functional materials for the efficient separation of hydrocarbons with similar physicochemical properties.

Keywords: Adsorptive separation; Hydrocarbon; Metal-organic frameworks; Iso-butene/iso-butane; Purification.