ADSORPTION SCIENCE & TECHNOLOGY
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2023
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IF 2.9
Lingzhi Yang,Wenpeng Xie,Qiuju Fu,Liting Yan,Shuo Zhang,Huimin Jiang,Liangjun Li,Xin Gu,Dandan Liu,Pengcheng Dai,Qingbin Zheng,Xuebo Zhao
The separation of acetylene (C2H2) from carbon dioxide (CO2) and the purification of ethylene (C2H4) from C2H2 are quite essential processes for the chemical industry. However, these processes are challenging due to their similar physical properties, including molecule sizes and boiling points. Herein, we report an N-rich cage-based microporous metal-organic framework (MOF), [Cd5(Tz)9](NO3) (termed as Cd-TZ, TZ stands for tetrazole), and its highly efficient separation of C2H2/CO2 and C2H2/C2H4. Single-component gas adsorption isotherms reveal that Cd-TZ exhibits high C2H2 adsorption capacity (3.10 mmol g-1 at 298 K and 1 bar). The N-rich cages in Cd-TZ can trap C2H2 with a higher isosteric heat of adsorption (40.8 kJ mol-1) than CO2 and C2H4 owing to the robust host-guest interactions between the noncoordinated N atoms and C2H2, which has been verified by molecular modeling studies. Cd-TZ shows a high IAST selectivity for C2H2/CO2 (8.3) and C2H2/C2H4 (13.3). The breakthrough simulations confirm the potential for separating C2H2/CO2 and the purification of C2H4 from C2H2.
研究领域:
化学工程
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材料科学
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高影响因子
ACS Applied Polymer Materials
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2025
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IF 4.7
Yucheng Wang,Fangzhe Lu,Juanqin Xue
Flexible covalent organic frameworks (COFs) are attractive due to their unique kinetic properties. However, their accessibility remains limited. In particular, it is challenging to control the flexibility of COFs, and the effects of different flexibilities on the properties of COFs are rarely revealed. In this work, three hydrazone-linked COFs with increasing flexibility were designed and synthesized by adjusting the flexibility of the hydrazide linker step-by-step. Through static adsorption and dynamic separation experiments, remarkable differences in adaptation among three COFs are revealed. The gas adsorption experiment shows that Ta-DMTH-COF has the best purification ability of C2H2/C2H4, and the selectivity of ideal adsorbed solution theory can reach 5.17, which is much higher than the other two COFs. This paper studied a flexible strategy of COFs by adjusting their connectors, and the influence of different flexibilities on the performance of COFs is analyzed, which provides an idea for the research and development of this kind of dynamic porous material.
研究领域:
材料科学
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分离技术
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共价有机框架
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气体净化
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Nature Communications
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2022
·Vol. 13
·期 1
·1-9
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IF 17.694
Liu Yuan,Liu Junhui,Xiong Hanting,Chen Jingwen,Chen Shixia,Zeng Zheling,Deng Shuguang,Wang Jun
Efficient adsorptive separation of acetylene (C 2 H 2 ) from carbon dioxide (CO 2 ) or ethylene (C 2 H 4 ) is industrially important but challenging due to the identical dynamic diameter or the trace amount. Here we show an electrostatic potential compatible strategy in a nitroprusside-based Hofmann-type metal-organic framework, Cu(bpy)NP (NP = nitroprusside, bpy = 4,4’-bipyridine), for efficient C 2 H 2 separation. The intruding cyanide and nitrosyl groups in undulating one-dimensional channels induce negative electrostatic potentials for preferential C 2 H 2 recognition instead of open metal sites in traditional Hofmann-type MOFs. As a result, Cu(bpy)NP exhibits a 50/50 C 2 H 2 /CO 2 selectivity of 47.2, outperforming most rigid MOFs. The dynamic breakthrough experiment demonstrates a 99.9% purity C 2 H 4 productivity of 20.57 mmol g −1 from C 2 H 2 /C 2 H 4 (1/99, v / v ) gas-mixture. Meanwhile, C 2 H 2 can also be captured and recognized from ternary C 2 H 2 /CO 2 /C 2 H 4 (25/25/50, v/v/v ) gas-mixture. Furthermore, computational studies and in-situ infrared spectroscopy reveal that the selective C 2 H 2 binding arises from the compatible pore electro-environment generated by the electron-rich N and O atoms from nitroprusside anions.
研究领域:
材料科学
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化学工程
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2023
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IF 8.6
Yan Zhang,Xiaoyu Deng,Xinran Li,Xing Liu,Peixin Zhang,Lihua Chen,Zhihong Yan,Jun Wang,Shuguang Deng
Highly selective separation of acetylene from various other gases (e.g., carbon dioxide and methane) is of great importance in the petrochemical industry but remains a challenge due to their similar sizes and physical properties. Herein, we reported a microporous metal − organic framework Zn 4 O(NTB) 2 (H 3 NTB = 4,4′,4″-nitrilotribenzoicacid acid), features oxygen binding sites explored for C 2 H 2 capture and separation. A high C 2 H 2 uptake of 2.62 mmol g −1 combined with excellent selectivity of C 2 H 2 /CO 2 (4.8) and C 2 H 2 /CH 4 (21.6) under ambient conditions (i.e., 50:50 mixture at 298 K and 1 bar) was realized. Moreover, the grand canonical Monte Carlo (GCMC) simulations and first-principles density functional theory (DFT) calculations have identified that the high C 2 H 2 capture and selectivity ascribe to oxygen sites on the pores (C–H…O interaction). Dynamic breakthrough experiments comprehensively demonstrate that Zn 4 O(NTB) 2 is a promising adsorbent for practical C 2 H 2 /CO 2 and C 2 H 2 /CH 4 separation.
研究领域:
化学工程
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材料科学
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石油化工
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
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IF 9.7
Hui Kang,Chen-Ning Li,Lifei Yin,Jiabao Gui,Meng Wang,Yang Chen,Jinping Li,Libo Li
The separation of carbon dioxide (CO 2 ) from acetylene (C 2 H 2 ) is crucial but highly challenging due to their similar molecular dimensions and physicochemical properties. In contrast to C 2 H 2 -selective adsorbents, CO 2 -selective adsorption strategy substantially reduces energy consumption by eliminating the need for additional C 2 H 2 desorption steps. However, the development of CO 2 -selective adsorbents capable of reversing C 2 H 2 /CO 2 separation remains limited and requires further exploration. Herein, we report a porous coordination polymer, [Cu(5-NH 2 -ipa)(pia)], featuring an interdigitated structure with one-dimensional corrugated channels to directly purify C 2 H 2 . Adsorption results indicate that at 298 K and 1.0 bar, [Cu(5-NH 2 -ipa)(pia)] exhibits a CO 2 /C 2 H 2 uptake ratio of 2.09 and IAST (Ideal adsorbed solution theory) selectivity of 10.9. It possesses optimally sized pores with an electrostatic potential that is highly complementary to the electrostatic properties of CO 2 , enabling preferential CO 2 adsorption through strong electrostatic interactions and hydrogen bonding. This result is well supported by molecular simulation and theoretical calculations. Furthermore, experimental breakthrough tests demonstrate that high-purity CO 2 can be directly obtained from CO 2 and C 2 H 2 mixtures. This work paves the way for the future development of advanced porous materials and inspires their use for CO 2 -selective capture from C 2 H 2 .
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CHINESE JOURNAL OF STRUCTURAL CHEMISTRY
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2024
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IF 5.9
Yongheng Ren,Yang Chen,Hongwei Chen,Lu Zhang,Jiangfeng Yang,Qi Shi,Lin-Bing Sun,Jinping Li,Libo Li
The identical molecular size and similar physical properties of carbon dioxide (CO 2 ) and acetylene (C 2 H 2 ) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO 2 and C 2 H 2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO 2 and C 2 H 2 , realizing the inverse separation of zeolite from selective adsorption of C 2 H 2 to selective adsorption of CO 2 . Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C 2 H 2 between the cages while ensuring the transfer of CO 2 , increasing their diffusion differences in pore channels and leading to the CO 2 /C 2 H 2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO 2 distribution in K-5A- β is significantly higher than that of C 2 H 2 . Dynamic breakthrough experiments verify the excellent performance of material in practical CO 2 /C 2 H 2 separation, for CO 2 /C 2 H 2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C 2 H 2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO 2 and C 2 H 2 .
研究领域:
材料科学
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化学工程
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ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2025
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IF 11.3
Mingming Wang,Yurui Fan,Qinyuan Hong,Wenjun Huang,Xing Han,Zan Qu,Naiqiang Yan,Haomiao Xu
Mercury emissions from acetylene hydrochlorination processes in polyvinyl chloride (PVC) production pose severe environmental risks yet remain poorly quantified due to methodological limitations in high-reactivity C2H2/HCl atmospheres. We reported an advanced operando mercury speciation platform named PVC-OHM, engineered through systematic optimization of the Ontario Hydro method (OHM), achieving simultaneous real-time detection of elemental mercury (Hg0) and divalent mercury (Hg2+) with unprecedented sensitivity (0.12 μg/m3) under industrially relevant conditions. Our mechanistic investigation reveals three dominant mercury escape pathways: (1) thermal desorption, wherein localized hotspots accelerate HgCl2 decomposition and elevate the saturated vapor pressure at carbon-mercury interface (from 0.9 to 20.3 atm), contributed to 80% of total Hg loss; (2) C2H2 driven reductive decomposition of HgCl2 catalyst at carbon–mercury interfaces, responsible for 65–78% of Hg0 emissions and (3) excess chlorine adsorption-induced desorption ([HgCl2/AC] Cl5, Eads > 0) accounting for >10% of Hg2+ emissions. Quantitative tracking demonstrates alarming mercury loss of per gram catalyst (5 wt % Hg) reached as 3.08 mg Hg0 and 9.01 mg Hg2+, directly linked to localized thermal gradients (ΔT = 250–300 °C) at reaction hotspots. This work establishes the first experimentally validated framework for mercury fate prediction in carbide-based PVC synthesis, providing actionable strategies for emission control through hotspot mitigation and coordination environment optimization.
研究领域:
环境化学
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化学工程
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催化科学
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污染控制
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工业排放
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PubMed
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JOURNAL OF MEMBRANE SCIENCE
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2026
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IF 8.8
Jianfa Liu,Yang Liu,Haonan Luo,Hui-Fang Wang,Zhenggong Wang,Jian Jin,Zheng Niu,J. Liu,Y. Liu,H. Luo,H. Wang,Z. Wang,J. Jin,Z. Niu
Hybrid membranes combine the excellent processability of polymer with the superior permeability and selectivity of porous fillers, demonstrating exceptional separation performance. However, interfacial incompatibility remains a fundamental challenge in such systems. Herein, we report a strategy incluced by molecular adsorption sites to mitigate interfacial incompatibility issues. MOF has been proved as a efficient ethyne adsorbents and applied in the separation of C 2 H 2 /C 2 H 4 . Its inorganic adsorption units, which exhibit a high affinity for ethyne, were uniformly high-quality dispersed within a polymer matrix to enable efficient C 2 H 2 /C 2 H 4 separation. The optimized hybrid membrane exhibits a 249% enhancement in C 2 H 2 /C 2 H 4 perm-selectivity compared to the pristine polymer membrane, while maintaining competitive C 2 H 2 permeability. This performance surpasses that of most reported hybrid membranes incorporating conventional fillers. Remarkably, the membranes maintain stable operation under varying pressures and prolonged testing durations. This study presents a facile yet effective strategy for fabricating high-performance gas separation membranes through the dispersion of molecular adsorption sites, opening new avenues for advanced alkyne/olefin separation.
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Inorganic Chemistry Frontiers
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2025
·Vol. 12
·期 12
·4007-4018
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IF 6.4
Hong-Juan Lv,Yunhui Zhai,Ying-Ying Xue,Jiao Lei,Wenyu Yuan,Quan-Guo Zhai
Adsorption-based separation techniques are pivotal in the purification of C2H2, leveraging their eco-friendly and energy-efficient attributes. However, the reusability of adsorbents is highly restricted by the trade-off between adsorption capacity and adsorption enthalpy, which is required to be urgently addressed. Herein, we demonstrated that the implantation of distortable ligands with functional groups is efficient in solving the above issue. The functional groups provided binding sites for C2H2 adsorption, while the distortable ligands optimized the pore structures to reduce adsorption enthalpy, thus balancing the trade-off between adsorption capacity and enthalpy. A series of ultra-microporous MOFs was successfully constructed by employing different pyridine ligands. The adsorption capacity of SNNU-504 after optimization was effectively enhanced, while the adsorption enthalpy hardly increased due to the adjustable ligand torsion angle. Breakthrough experiments and GCMC simulations further verified the potential C2H2/CO2 separation applications.
研究领域:
材料科学
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化学工程
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吸附技术
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分离科学
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纳米多孔材料
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PROCEEDINGS OF THE COMBUSTION INSTITUTE
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2025
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IF 5.2
Zhaohan Chu,Zhongkai Liu,Changyang Wang,Long Zhao,Bin Yang
An experimental study was conducted to investigate the weight growth routes from o -methylphenyl radical ( o -CH 3 C 6 H 4 ) to indene. o -Nitrosotoluene served as the precursor for o -methylphenyl radicals in this study. Co-pyrolysis of o -methylphenyl radical/C 2 H 2 and o -methylphenyl radical/C 2 H 4 was investigated utilizing the chemical microreactor and synchrotron vacuum ultraviolet photoionization mass spectrometry. Sampled mass-specific photoionization efficiency (PIE) curves were employed to identify the aromatic species, elucidating interactions between o -methylphenyl radicals and C 2 species. The species detected at m/z = 116 and 118, essential for understanding the reaction mechanism, were identified via matching photoionization cross-sections and adiabatic ionization energies with literature and theoretical values. Specifically, indene and its isomer o -methylphenylacetylene ( m/z = 116) were determined in the reaction of o -methylphenyl radical with C 2 H 2 , while indene and o -methylstyrene ( m/z = 118) were identified in the reaction of o -methylphenyl radical with C 2 H 4 . By combining the identified intermediate species with previous literature basis, the formation pathways for indene, originating from o -methylphenyl radical were discussed in both reaction systems, providing further insights for understanding the indene formation pathways.
研究领域:
物理化学
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燃烧化学
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分子反应动力学
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质谱分析
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有机反应机理
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高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
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2026
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IF 3.5
Cai He,Bingfeng Guo,Tong Li,Xiaoxia Jia,Yong Wang,Zhiyun Xiao
A rigid–flexible Zn-DMOF was developed for selective C 2 H 2 /CO 2 separation. • Activation-induced pore contraction enabled dynamic recognition of C 2 H 2 . • Zn-chdc-DABCO retained high C 2 H 2 uptake but greatly improved C 2 H 2 /CO 2 selectivity. • Efficient breakthrough separation was maintained under varying flow rates and humidity. Separating C 2 H 2 from CO 2 is challenging because of their similar sizes and physicochemical properties. Adsorption-based separation using metal–organic frameworks (MOFs) offer a promising alternative. Here, a rigid–flexible framework strategy is used to introduce guest-discriminating dynamic recognition into a 1,4-diazabicyclo[2.2.2]octane (DABCO)-based MOF (DMOF) platform by replacing rigid 1,4-benzenedicarboxylate with flexible trans-1,4-cyclohexanedicarboxylate, affording Zn-trans-1,4-cyclohexanedicarboxylic acid (chdc)-DABCO. Activation induces pore contraction and generates a confined environment that selectively strengthens C 2 H 2 binding while leaving CO 2 largely unaffected. As a result, Zn-chdc-DABCO preserves a C 2 H 2 uptake comparable to that of Zn-DMOF at 298 K and 100 kPa, yet displays markedly enhanced affinity toward C 2 H 2 , a distinct gate-opening response to C 2 H 2 , and little framework response toward CO 2 . The zero-coverage isosteric heat of adsorption reaches 43.9 kJ·mol –1 for C 2 H 2 , substantially higher than that for CO 2 (29.3 kJ·mol –1 ), and the equimolar C 2 H 2 /CO 2 ideal adsorbed solution theory selectivity reaches 8.2, more than four times that of Zn-DMOF. Dynamic breakthrough experiments further confirm efficient separation under mixed-gas, variable-flow, and humid conditions. This work shows that rigid–flexible cooperative design offers an effective route to overcoming the capacity/selectivity trade-off in difficult gas separations. A rigid–flexible Zn-DMOF was engineered to enable activation-induced pore contraction and guest-discriminating dynamic recognition, thereby achieving enhanced selective C 2 H 2 /CO 2 separation with efficient C 2 H 2 recovery. Download: Download high-res image (204KB) Download: Download full-size image
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Small
·
2026
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IF 11.8
Zhenliang Zhu,Jianfei Xiao,Ruiyao Li,Yaoqi Huang,Shaojun Yuan
Ultramicroporous MOFs capable of simultaneously separating C 2 H 6 /C 2 H 4 and C 2 H 2 /CO 2 mixtures remain rare due to the stringent requirements on pore confinement and adsorption-site distribution. Here, we report a dual-ligand engineered porphyrin-based framework, Zn-TCPP-mtz, constructed from Zn 2+ nodes, tetrakis(4-carboxyphenyl)porphyrin (TCPP), and 5-methyl-1H-tetrazole (mtz). The incorporated mtz ligands bridge adjacent porphyrin layers and, together with interlayer hydrogen-bonding interactions, result in a compact stacking arrangement featuring 1D ultramicropores (7.2 × 4.8 Å 2 ) decorated with N/O functional sites and hydrophobic methyl groups. This tailored pore environment enables Zn-TCPP-mtz to adsorb 2.63 and 2.56 mmol g −1 of C 2 H 6 and C 2 H 4 , respectively, as well as 3.14 and 1.89 mmol g −1 of C 2 H 2 and CO 2 at 298 K and 1 bar, achieving selectivities of 1.5 for C 2 H 6 /C 2 H 4 and 3.1 for C 2 H 2 /CO 2 . Dynamic breakthrough experiments confirm one-step production of high-purity C 2 H 4 (>99.9%) and C 2 H 2 (>99.5%) with productivities of 3.0 and 16.3 L kg −1 , respectively. DFT calculations reveal that the ultramicroporous channels provide well-defined interaction sites that stabilize C 2 H 6 over C 2 H 4 and C 2 H 2 over CO 2 through multiple dispersion-dominated contacts. This study demonstrates that the dual-ligand strategy can be extended to construct porphyrin-based frameworks with controlled pore architectures and stable adsorption environments, enabling the integration of multiple C 2 gas separations within a single material platform.
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高影响因子
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