PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
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2023
·Vol. 120
·期 27
·e2219179120
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IF 11.1
Yuanji Shi,Hongxin Mu,Jiaqian You,Chenglong Han,Huazai Cheng,Jinfeng Wang,Haidong Hu,Hongqiang Ren
The global ecological crisis of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water has gradually shifted from long-chain to short-chain PFASs; however, the widespread established PFAS adsorption technology cannot cope with the impact of such hydrophilic pollutants given the inherent defects of solid–liquid mass transfer. Herein, we describe a reagent-free and low-cost strategy to reduce the energy state of short-chain PFASs in hydrophobic nanopores by employing an in situ constructed confined water structure in activated carbon (AC). Through direct (driving force) and indirect (assisted slip) effects, the confined water introduced a dual-drive mode in the confined water–encapsulated activated carbon (CW-AC) and completely eliminated the mass transfer barrier (3.27 to 5.66 kcal/mol), which caused the CW-AC to exhibit the highest adsorption capacity for various short-chain PFASs (C-F number: 3-6) among parent AC and other adsorbents reported. Meanwhile, benefiting from the chain length– and functional group–dependent confined water–binding pattern, the affinity of the CW-AC surpassed the traditional hydrophobicity dominance and shifted toward hydrophilic short-chain PFASs that easily escaped treatment. Importantly, the ability of CW-AC functionality to directly transfer to existing adsorption devices was verified, which could treat 21,000 bed volumes of environment-related high-load (~350 ng/L short-chain PFAS each) real drinking water to below the World Health Organization’s standard. Overall, our results provide a green and cost-effective in situ upgrade scheme for existing adsorption devices to address the short-chain PFAS crisis.
研究领域:
环境科学
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材料科学
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化学工程
✓ 已验证
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
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IF 7.1
Zhuqian Xiao,Qian Zhao,Qin Li,Yurui Wang,Huilin Zheng,Hongpeng Wang,Jun Huang,Jianwei Mao
The current manufacture of (carboxymethyl)cellulose (CMC) requires a large amount of solvents, severely resulting in environmental impacts and a laborious separation process. Herein, a “green” synthetic route employing a mechanochemistry strategy was addressed to prepare CMC promoted by minute surface-confined water. The mechanical forces (shear and strain) from ball collisions facilitated the formation of disordered regions, promoting the water-holding capacity of cellulose. Together, water molecules permeated the impact structure and were locked by surface hydroxyls, intensifying the chemical accessibility. The resultant CMC possessed a wide degree of substitution within 0.38–1.03 and a maximum yield of 46.1% under optimal mechanochemical conditions. Density functional theory revealed that Gibb’s free energy (ΔGTS) of hydroxyl activation was approximately −1.73 eV on the surface of dry cellulose. In comparison, ΔGTS was reduced to −3.37 eV upon intervention of water. The reactivity sensitivity of hydroxyls was C2 > C6 > C3 on the surface of highly hydrated cellulose. The high concentration (1200 μg/mL) of CMC was not significantly toxic to HepG2 cells (apoptosis rate of less than 4.0%), demonstrating the excellent biocompatibility of CMC prepared by this strategy. This mechanochemical method opened a safe and environmentally friendly avenue to produce CMC without sacrificing excess reagents.
研究领域:
材料科学
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化学工程
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环境科学
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生物技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
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2025
·
IF 6.5
Hongbing Wang,Xiaolin Zhou,Jun Chen,Dongping Wang,Yunxi Yao,Yifei Yang
Confined water clusters within the microporous framework of zeolite positively or negatively influence the catalytic reaction rates and selectivities, because of their steric effects to the reactive intermediates and transition states differently. In this study, a series of supported Pt-zeolites (e.g. 1Pt/USY, 1Pt/MOR, 1Pt/Beta, 1Pt/ZSM-5 and 1Pt/ZSM-35) with the analogous Pt cluster size and the concentration of Brønsted acid sites (BAS) and the different pore structures were employed to investigate the catalytic roles of confined water clusters during H 2 -HDO isotope exchange. The comparable reactive environments upon these bifunctional Pt catalysts enable them to share the identical reaction pathway during hydrogen isotope exchange. Specifically, water clusters are protonated on BAS to deliver deuteron and the subsequent hydrogen isotope exchange occurs at the interface of metal-water clusters by a synchronously bidirectional transfer, leading to the similar activation energy of 30.5 ± 4.0 kJ mol −1 . Nevertheless, the pore architectures of as-used zeolites affect the structure of confined water clusters in the form of one-dimensional oligomeric chains or three-dimensional bulk-like networks within the microporous frameworks, which constrains the hydrogen intrapore diffusion in the sub-nanometer scale and the subsequent reaction kinetic events to the different extents. As a result, the measured reaction rates upon these Pt-zeolite catalysts follow this order: 1Pt/USY>1Pt/MOR>1Pt/Beta>1Pt/ZSM-5>1Pt/ZSM-35. Collectively, this work shows that how the confined water within microporous environment affects the catalytic process, which also offers the mechanistic understanding of reaction chemistry in the restricted space.
研究领域:
催化
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物理化学
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材料科学
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化学反应工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SPECTROSCOPY
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2022
·
IF 3.588
Biao Ma,Wensheng Cai,Xueguang Shao
Analysis of the confined water in hydrogels is essential for understanding the chemical and physical properties. Methods to quantify the content and study the structure of water in hydrogel using near-infrared (NIR) spectroscopy were proposed. The NIR spectra of poly-N,N-dimethylacrylamide (PDMAA) hydrogel with different water contents were measured at different temperatures. A partial least squares (PLS) model was established using the spectra of the samples with water content (wh) from 0.9 to 387.6%. Continuous wavelet transform (CWT) was adopted to calculate the resolution enhanced spectra from which the spectral features of water species with free OH (S0) and with one or two hydrogen bonds (S1 and S2) was obtained. The variation of these water species with water content suggests the existence of the water molecules bonding to NH groups by one hydrogen bond (S1NH) and hydrating the CH groups of the polymer network and bulk-like water. Moreover, the variation of water structures with temperature shows that the release of bulk-like water occurs in the phase transition of the hydrogel, but the S1NH and the hydration water stay unchanged. The former explains the sudden volume shrinkage for the phase transition and the latter may be the reason for the shape memory effect in the repeated swelling and deswelling of hydrogels.
研究领域:
分析化学
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高分子科学
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光谱学
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材料科学
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物理化学
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
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2022
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IF 7.336
Pengfei Sun,Wenxiu Liu,Daiwen Yang,Yan Zhang,Weiming Xiong,Sha Li,Jiajia Chen,Jinghua Tian,Li Zhang
In aqueous electrolyte, the hydration of solvated zinc ions and the unstable deposition interface exacerbate the accumulation of Zn dendrites and the generation of by-products, making it difficult to achieve highly reversible and long-life Zn-ion batteries (ZIBs). Herein, a high-modulus agarose gel electrolyte (AGE) with greatly suppressed H 2 O molecule mobility, is designed to overcome the above challenges. The ample hydroxyl (-OH) functional groups on the double helix chain of the AGE can capture and anchor H 2 O molecules via hydrogen bonding, thus fundamentally regulating the coordination environment of Zn 2+ and enhancing the stability of deposition interface. Moreover, the -OH functional groups can also effectively immobilize sulfate ions and largely confine their free diffusion, thereby greatly inhibiting the formation of zinc hydroxysulfate by-product. As such, the dendrite issue and side reactions can be significantly mitigated using our designed AGEs, holding great promise for ZIBs with extended cycling durability and high safety.
研究领域:
电化学
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储能材料
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电池技术
✓ 已验证
DOI
高影响因子
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