Industrial Chemistry & Materials最新文献

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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.

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.

The separation of C₂H₂/CO₂ mixtures for acetylene purification presents both industrial significance and fundamental challenges due to their nearly identical kinetic diameters and similar physical properties. This study demonstrates the effectiveness of ultramicroporous metal–organic frameworks (MOFs) in addressing this challenge through precise pore confinement effects. We introduce two ultramicroporous materials, Cu(cyhdc) and Cu(bdc), and assess their ability to capture C₂H₂. Under ambient conditions, Cu(cyhdc) and Cu(bdc) exhibit C₂H₂ uptakes of 1.92 mmol g⁻¹ and 1.44 mmol g⁻¹, respectively. The most promising candidate is Cu(cyhdc), which possesses a C₂H₂/CO₂ selectivity of 8.45 at 298 K and 1 bar. Grand canonical Monte Carlo simulations revealed that the enhanced performance originates from multiple van der Waals interactions between C₂H₂ molecules and the curved cyclohexane-derived pore walls of Cu(cyhdc). Importantly, dynamic breakthrough experiments and scalable synthesis processes validated the practical separation potential of Cu(cyhdc) for C₂H₂/CO₂ mixtures. This work provides both mechanistic insights into gas–framework interactions and a potential solution for energy-efficient acetylene purification.

Keywords: C₂H₂/CO₂ separation; Ultramicroporous; Metal–organic framework; Pore confinement; Scalable synthesis.

On-line detection of additive concentrations in acidic copper (Cu) electroplating solution, including the suppressor, accelerator and leveler, is crucial for the industrial production of integrated circuit metal interconnections. For this purpose, a portable electrochemical microfluidic workstation (EMW) is developed. The polymer electrochemical microfluidic chip is designed and fabricated by 3D printing, in which a liquid mixer is integrated with an electrochemical microcell. The asymmetrically distributed herringbone microstructures in the microchannels (width: 400 μm, height: 300 μm, length: 4 cm) ensure the highly efficient mixture of solutions. In the electrochemical microcell, a 12.5 μm radius platinum ultramicroelectrode (Pt UME) acts as the working electrode. Based on the suppressing or accelerating effects of the additives on Cu electroplating, the calibration curves can be obtained by the stripping charge of electrodeposited Cu. Thus, the concentration of each additive in the acidic Cu electroplating solution can be detected on line and adjusted in time. The solution volume needed for each additive is approximately 220 μL. The detection error is lower than 10%, meeting the analytic requirements in industry. The automated EMW has the potential to replace the current manual cyclic voltammetry stripping (CVS) employed in lab analysis.

Keywords: Electrochemical microfluidic workstation; On-line detection of additive concentration; Microfluidic chip; Ultramicroelectrode; Acidic copper electroplating.

Ultramicroporous carbon materials with precisely engineered pore structures offer a promising pathway for the challenging separation of fluorinated gases with similar physicochemical properties, such as C₃F₆ (fluorinated propylene) and C₃F₈ (fluorinated propane). In this work, we report the synthesis of CO₂-activated porous carbon adsorbents derived from a precursory resin and systematically investigate their molecular sieving behavior for C₃F₆/C₃F₈ mixtures. Through controlled thermal pyrolysis and stepwise CO₂ activation, we tailored ultramicropore size distributions to selectively exclude or admit target molecules. Adsorption studies reveal that optimal CO₂ activation yields pore sizes that enable effective separation of C₃F₆ from C₃F₈, achieving efficient molecular sieving due to size exclusion effects. Excessive activation, however, generates larger pores that diminish selectivity due to nonspecific affinity for both gases. The findings highlight the importance of ultramicropore control for energy-efficient separation of fluorinated hydrocarbons and provide insights for designing advanced adsorbents for industrial gas purification.

Keywords: Electronic specialty gas (ESGs); Adsorption separation; Phenolic resin-derived carbon; Molecular sieving; C₃F₆/C₃F₈.

PGMEA is widely used as a solvent and diluent for photoresists, yet developing an efficient resin that simultaneously resists organic dissolution and removes trace metal ions presents a significant challenge. To overcome this, a novel sulfonated hyper-cross-linked resin (2-CS-DVB-SO₃H) was synthesized through a multi-step process involving the preparation of a Cl-functionalized gel polymer, followed by sulfonation and post-crosslinking. The effects of the monomers, crosslinking degree, sulfonation degree, dosage, adsorption temperature, and resin stability on its purity performance were discussed. The resulting resin demonstrated exceptional stability in organic media and effectively purified PGMEA under optimized conditions (30% crosslinking, 4.69% S content, and 0.2 g mL⁻¹ resin dosage), with Ti, Co, Ni, and Cu metal ion concentrations reduced below 10 ppb. This process elevated PGMEA purity from 98.90% to 99.48%. Thermodynamic analysis revealed the adsorption to be non-spontaneous. The resin maintained chemical stability in PGMEA within 18 h. FT-IR and XPS data identified ion exchange, electrostatic interactions and lone electron pair coordination between sulfonic acid groups and metal ions as the binding mechanisms. The hydrogen bonds formed between Cl⁻ on the resin and hydroxyl groups in methanol (as organic impurities) were considered the primary factor responsible for enhancing the purity of PGMEA. These results collectively establish 2-CS-DVB-SO₃H as a robust and reliable material for metal ion removal in PGMEA purification, thereby improving the purity of photoresist solvents and potentially enhancing photoresist performance.

Keywords: Sulfonated resin; PGMEA; Metal ion removal; Purification mechanisms.