Industrial Chemistry & Materials最新文献

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.

This perspective identifies the carbon needs of the chemical and transport industries in the short-to-medium term, categorizes the available renewable alternative carbon sources (biomass, waste-plastics and CO₂) to fossil carbon and discusses their usability and potential for the short-, medium- and long-term use. Given the constraints to the use of biomass (grown on purpose and waste) and the limited overall amount of waste plastics, CO₂ is the most abundant and at-hand source of renewable carbon. The conversion of CO₂ into chemicals, materials and energy products is discussed for meeting the energetic and hydrogen demands. The use of solar energy as a primary energy source and water as a proton and electron source in recycling carbon via CO₂ conversion into energy products is also elucidated. E-fuels and solar-fuels are compared for their commercialization, and the benefits of co-processing CO₂ and water (in electrochemical, photochemical and photoelectrochemical processes) instead of producing green-H₂ for CO₂ reduction are emphasized.

Keywords: Carbon dioxide as source of renewable carbon; Carbon cyclic economy; Photochemistry; Photoelectrochemistry; E-fuels; Solar-fuels

Heteroatom-doped hierarchical porous carbon materials demonstrate significant promise for energy storage applications. In this paper, nitrogen-doped hierarchical porous carbon (NPC) materials were synthesized by one-step carbonization process using agar as the carbon precursor, urea as the nitrogen precursor, and KHCO₃ as the activating agent. Owing to the combined influence of substantial nitrogen and oxygen functional groups, interconnected hierarchical porous structure and large specific surface area, the NPC-600 electrode delivers a high specific capacitance of 450 F g⁻¹ and remarkable cyclic stability. Moreover, the NPC-600//NPC-600 symmetrical supercapacitor delivers an energy density of 29.41 Wh kg⁻¹ and good cyclic performance. More interestingly, a zinc ion hybrid capacitor (ZIHC) constructed with NPC-600 as the positive electrode achieves a capacitance of 368.78 F g⁻¹ (163.9 mAh g⁻¹), an energy density reaching 120.75 Wh kg⁻¹ and superior cyclic characteristics. The research affords a straightforward way for fabricating heteroatom-doped porous carbon as electrode for supercapacitor and ZIHCs.

Keywords: Hierarchical porous carbon; KHCO₃; Agar; Supercapacitor; Zinc ion hybrid capacitor.

The concentrations of CO₂ emitted from different CO₂ sources vary significantly. Thus, processes capable of accommodating a broad range of CO₂ concentrations, from 0.04% (air) to 10% (power plants), must be developed to achieve carbon neutrality. In this study, we developed a two-step CO₂ capture and hydrogenation system by employing Rb-oxide-incorporated zeolites as CO₂ adsorbents and Ni/CeO₂ or Cu/ZnO/Al₂O₃ as catalysts for CO₂ hydrogenation. This process is suitable for continuous operation over a temperature swing of 40–200 °C. Notably, this system can operate at low temperatures (below 200 °C) using a simple temperature-swing process in the presence of O₂. Compared with more than 100 previously reported systems that can convert CO₂ including O₂ to green fuels such as CO or CH₄, the proposed system achieved the best CO₂ conversions to CH₄ and CO.

Keywords: Direct air capture (DAC); Zeolite sorbent; Temperature swing adsorption (TSA); Methanation; Reverse water-gas shift (RWGS).

Aryl sulfonate ester modified polystyrenes with different substituents (X–SEPS, X = H–, MeO–, and CN–) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The excellent thermal stability and film-forming capability of these three polymers suggest that they can satisfy the lithography process and are candidates for resist materials. Comparative electron beam lithography (EBL) demonstrates that the three resists (H–SEPS, MeO–SEPS and CN–SEPS) exhibit different EBL performances. Calculation of bond energies for the model compounds suggests that the influence of substituent groups on the bond energy is not the reason for the differences in sensitivity. Results obtained using a fully automated dissipative quartz crystal microbalance (QCM) analyzer confirm that the influence of substituent groups on the solubility behavior of resist films in developers leads to different photolithographic performances. The H–SEPS resist exhibits better comprehensive performance than the MeO–SEPS and CN–SEPS resists, achieving an 18 nm line/space (L/S) pattern and a 10 nm line/4 space (L/4S) semi-dense pattern by EBL at doses of 3200 and 2800 μC cm⁻², respectively. Further extreme ultraviolet lithography (EUVL) demonstrates the capability of H–SEPS resist to form 22 nm half-pitch (HP) patterns. The detailed study of the photochemical reaction and patterning mechanism suggests that the decomposition of sulfonate ester groups into polar sulfonic acid groups, along with a rearrangement, leads to a solubility switch of resist films in the developer.

Keywords: Nonchemically amplified resist; Reversible addition-fragmentation chain transfer polymerization; Aryl sulfonate; Electron beam lithography; Extreme ultraviolet lithography.

The semiconductor manufacturing industry imposes stringent requirements on the metal ion content of photoresist resin monomers. Tris(2-carboxyethyl) isocyanurate (H₃tci), a critical raw material for photoresist resin monomers, inevitably incorporates metal ions during production. However, its inherent carboxyethyl groups form stable coordination complexes with Cr(III), hindering the semiconductor-grade resin monomer production. To achieve the ultra-deep removal of Cr(III) at ultra-trace concentrations, inspired by the hard–soft-acid–base theory, we systematically modulated the electron-rich sulfonic acid group on polymers via controlled sulfonation conditions to achieve a novel series of adsorption materials (St) with ultra-high Cr(III) adsorption affinity. The adsorption–recrystallization process using 6 g of St-V-15 could reduce the Cr(III) concentration in a solution containing 1 g of H₃tci from 840 ppb to 27.5 ppb. Furthermore, St-V-15 exhibited a maximum adsorption capacity of 145 mg g⁻¹ calculated using the Langmuir model and a rapid initial adsorption rate of 82.92 mg g⁻¹ min⁻¹ at 333 K. Additionally, St-V-15 demonstrated exceptional selectivity for Cr(III) over competing ions (e.g., K(I), Mg(II), Na(I) and Zn(II)) and maintained stable performance over at least 10 adsorption–desorption cycles. The superior performance originated from the chelation between Cr(III) and the sites of O atoms (S–O and SO) combined with the electrostatic interaction between deprotonated sulfonic acid groups and Cr(III). These results position St-V-15 as a promising adsorption material for ultra-trace Cr(III) removal in H₃tci, offering a cost-effective solution for semiconductor-grade resin monomer production for the very first time.

Keywords: Tris(2-carboxyethyl) isocyanurate; Complexed Cr(III); Ultra-trace; Cr(III) removal; Sulfonated polymers.

Ionic liquids (ILs) are a class of molten salts with a collection of exciting properties and have been employed for wide-ranging applications across chemistry, biology, and materials science. However, the high viscosity of ionic liquids challenges atomistic molecular dynamics (MD) simulations in studying their structure–property relationships on large spatiotemporal scales. Coarse-grained (CG) models provide insight into the microscopic structure and intermolecular interactions underlying various properties by eliminating unnecessary atomic details. The general protocol for proposing a new CG model is reviewed, including determination of CG representation and force field (FF) parameterization. Recent advances in polarizable CG models were discussed with the emphasis on Drude oscillators and QM-based polarizable models. An overview was given on some recent applications of machine learning (ML) techniques on development of CG potentials, including the utilization of an ML surrogate model for FF parameterization and the development of ML potentials. Applications and challenges of IL CG models in treating complex systems, including pure solvents, mixtures, biological systems, and electrochemically confined environments, were presented. Finally, prospects for the development of transferable IL CG models are highlighted to extend the applicability to more mesoscopic systems.

Keywords: Ionic liquids; Coarse-grained models; Polarization effect; Machine learning; Molecular dynamics simulation.