ADSORPTION SCIENCE & TECHNOLOGY
·
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
TOPICS IN CATALYSIS
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2023
·Vol. 66
·期 19
·1527-1538
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IF 3.6
Zhang Li,Men Yong,Wu Bin,Feng Yuanfen,Song Chao,Liu Shuang,Wang Jinguo,An Wei,Magkoev Tamerlan T.
Highly selective production of valuable ethylene from electrocatalytic CO 2 reduction reaction (ECO 2 RR) is particularly desirable yet challenging. Morphology engineering is an effective strategy for catalyst design, which can adjust the electronic structure of catalyst surface, change the adsorption behavior of critical reaction intermediates over catalyst surface, and thus regulate the activity of electrocatalytic CO 2 reduction reaction. In this work, we prepared copper phosphate catalysts with different morphologies and tested their catalytic activity for the ECO 2 RR in the flow cell. Compared with irregular flocculent aggregates, copper phosphate nanospheres exhibit a high and stable ethylene Faradaic efficiency of 47% with high current density of 350 mA·cm − 2 , which is higher than the 200 mA·cm − 2 required for industrial applications. The catalysts were extensively characterized by SEM, EDS, XRD, ICP-OES, XPS, BET and CO-TPD. Combining the characterization results and activity data, we found that the superior spherical morphology of copper phosphate can increase the electron density around Cu, stabilize the Cu + species on the surface through the electron transfer between P and Cu, and adjust the adsorption strength of CO intermediates (*CO) to enhance the productivity of C 2+ products. This work provides new insights into catalyst design for highly efficient C 2 H 4 production from the electrocatalytic CO 2 reduction reaction by tuning morphologies of Cu-based catalysts.
研究领域:
电化学
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材料科学
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催化
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化学工程
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高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2026
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IF 4.9
Ping Zhang,Qin-Wen Shi,Wen-Yuan Wu,Jun-Feng Bai
An anionic 3D MOF featuring 9-connected Ni 3 ( μ 3 -OH) secondary building units (SBUs), (Me 2 NH 2 ) 2 [Ni 6 (OH) 2 (Bpdc) 3 (4-Ptz) 6 ]·11H 2 O (NJTU-Bai90; NJTU-Bai denotes Nanjing Tech University Bai’s group), was hydrothermally synthesized using the bifunctional ligands bicyclo[1.1.1]pentane-1,3-dicarboxylic acid (H 2 Bpdc) and 4-(2H-tetrazol-5-yl)pyridine (4-HPtz). This MOF crystallizes in I-43 m space group and possesses intersecting 3D channels packed by trigonal-pyramidal and tetrahedral cages. Tailored for reversible C 2 H 6 adsorption and one-step purification of polymer-grade C 2 H 4 , NJTU-Bai90 not only has a high BET surface area of 1465.7 m 2 g −1 but also exhibits excellent stability in aqueous solutions at room temperature for at least one month. NJTU-Bai90 exhibits superior C 2 H 6 uptake (97.6 cm 3 g −1 at 298 K and 82.5 cm 3 g −1 at 308 K, both measured at 1 bar) in comparison with C 2 H 4 (85.5 cm 3 g −1 at 298 K and 68.4 cm 3 g −1 at 308 K, both measured at 1 bar). Remarkable IAST selectivity values (1.51 and 1.56, respectively) are maintained even at elevated temperatures. Furthermore, dynamic breakthrough experiments demonstrate that a C 2 H 6 /C 2 H 4 mixture (1/15, v/v) can be efficiently separated in one step and that polymer-grade C 2 H 4 yielding with a productivity of 19.1 mL g −1 at 298 K and 1 bar. The distinct retention times of C 2 H 6 and C 2 H 4 on NJTU-Bai90-packed separation columns further highlight the material’s great potential for industrial gas separation applications.
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Qiuling Chen,Shun Wang,Baoji Miao,Qiuping Chen
The creation of a Z-scheme heterojunction is a sophisticated strategy to enhance photocatalytic efficiency. In our study, we synthesized an In 2 S 3 /MnO 2 /BiOCl dual Z-scheme heterostructure by growing BiOCl nanoplates on the sheets of In 2 S 3 nanoflowers, situated on the surface of MnO 2 nanowires. This synthesis involved a combination of hydrothermal and solution combustion methods. Experiments and density functional theory (DFT) calculations demonstrated that the In 2 S 3 /MnO 2 /BiOCl composite exhibited notable photo reduction performance and photocatalytic stability. This was attributed to the pivotal roles of BiOCl and MnO 2 in the composite, acting as auxiliaries to enhance the electronic structure and facilitate the adsorption/activation capacity of CO 2 and H 2 O. The yield rates of CO, CH 4 , and C 2 H 4 over In 2 S 3 /MnO 2 /BiOCl as the catalyst were 3.94, 5.5, and 3.64 times higher than those of pure In 2 S 3 , respectively. Photoelectrochemical analysis revealed that the dual Z-scheme heterostructure, with its oxygen vacancies and large surface area, enhanced CO 2 absorption and active sites on the nanoflower/nanowire intersurfaces. Consequently, the dual Z-scheme charge transfer pathway provided efficient channels for boosting electron transfer and charge separation, resulting in high C 2 H 4 , CH 4 , and CO yields of formed and exihibits an promising photoreduction rate of CO 2 to CO (51.2 µmol/g.h), CH 4 (42.4 µmol/g.h) and C 2 H 4 (63.2 µmol/g.h), respectively. DFT, in situ Diffuse reflectance infrared fourier transform spectroscopy, and temperature-programmed desorption tests were employed to verify the intermediates pathway. The study proposed a potential photocatalytic mechanism based on these findings.
研究领域:
材料科学
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环境科学
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化学工程
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PubMed
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2025
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IF 4.7
Di-Ming Chen,Xue-Jing Zhang,Dong-Ying Shi,Lin Han
The separation of C 2 H 6 (ethane) from C 2 H 4 (ethylene) to produce C 2 H 4 with high purity is an important but challenging task in chemical industry due to their similar physical properties including molecular sizes and boiling points. Metal-organic frameworks (MOFs) with modifiable pore surroundings give new avenues for the development of functional materials for the targeted gas selective separation, especially for the design of C 2 H 6 -selective ones with simplified separation process and reduced energy consumption compared with those C 2 H 4 -selective ones. In the present study, a new Co(II)-based MOF featuring the formula of {[Co 2 (μ 2 -OH)(CPT) 2 (HCOO)](DMF) 3 (MeOH)} n ( 1 ) has been successfully prepared by reaction of Co(II) salt with a bifunctional organic ligand 4-(4 H -1,2,4-triazol-4-yl)benzoic acid (HCPT). The microporous pore surroundings of 1 feature high density of aromatic benzene ring and triazole groups coupled with uncoordinated O atoms, which collectively generate stronger interactions with C 2 H 6 molecules than with C 2 H 4 as revealed by the following dispersion corrected DFT calculations. As a result, the activated 1 shows a high C 2 H 6 uptake capacity of 109.1 cm 3 /g with a moderate high C 2 H 6 /C 2 H 4 (50:50) selectivity of 1.92 at 298 K and 1 bar, and such a separation ability was further supported by the breakthrough experiment. To further probe the underlying separation mechanism, the molecular dynamic simulation and DFT calculations were carried out, and the results coincide well with the experimental ones, which point out that the multiple synergistic interactions between C 2 H 6 molecules with the pore surface of 1 account for the high C 2 H 6 uptake capacity and C 2 H 6 /C 2 H 4 selectivity.
研究领域:
材料科学
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分离技术
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配位化学
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计算化学
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气体吸附
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2026
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IF 3.9
Jiaman Wang,Zekai Cui,Yuechang Wei,Zhiling Tang,Jing Xiong,Yingli Wang,Xiong Wang,Xuanzhen Li,Yunpeng Liu,Zhen Zhao
The efficiency of electron utilization and C–C coupling is crucial to the selectivity of photocatalytic CO2 reduction to multicarbon (C2+) hydrocarbon products. Herein, the multifunctional catalyst of TiO2-modified W18O49 nanospheres (TimWOx) was successfully fabricated by in situ growth hydrothermal method. The distinct interfacial energy between W18O49 and TiO2 can promote the charge redistribution at the asymmetric Ti–O–W active sites and facilitate the formation of an internal electric field (IEF). Photogenerated electrons driven by the IEF can improve the dynamic electron shuttling between Ti and W centers for enhancing electron utilization efficiency during CO2 photoreduction. TimWOx catalysts exhibit high activity for photocatalytic CO2 reduction to C2+ products, i.e., the yield and selectivity of C2H4 over Ti0.25WOx are 46.3 μmol·g–1 and 72.01%, respectively, which is 7.25 times that of pristine W18O49. Combined with the results of in situ diffuse reflectance infrared Fourier transform spectra and DFT calculations, the photocatalytic mechanism is proposed: the protonation the *OCCOH intermediate is key step for selective photocatalytic CO2 reduction into C2H4, and the energy barrier for the protonation of the *OCCOH intermediate is lowered by IEF-induced dynamic electron shuttling, which selectively steers the reaction pathway toward C2H4 formation. This work highlights the role of interfacial electric fields in guiding electron shuttling for selective photocatalytic C–C coupling, which benefits developing highly efficient photocatalysts.
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Qiang-Qiang Yang,Zhi-Han Ma,Qiang Zhang,Zi-Han Song,Hong-Xiang Nie,Jing-Jing Pang,Zhao-Quan Yao,Hongliang Huang,Min Feng,Tong-Liang Hu,Jian Xu
One-step adsorptive separation of high-purity ethylene (C 2 H 4 ) from the mixtures with ethane (C 2 H 6 ) or propylene (C 3 H 6 ) is of crucial importance in the petrochemical industry. Nevertheless, the development of porous materials that possess both high adsorption capacities and selectivities of C 2 H 6 and C 3 H 6 over C 2 H 4 is still a formidable challenge. Herein, we present a microporous pillar-layered metal–organic framework (MOF) that exhibits excellent uptake capacities of C 2 H 6 (4.73 mmol g −1 ) and C 3 H 6 (8.05 mmol g −1 ) at 298 K and 1 bar, leading to high adsorption selectivities for equimolar mixtures of C 2 H 6 /C 2 H 4 (1.6) and C 3 H 6 /C 2 H 4 (16.4), respectively. Breakthrough column experiments demonstrate that the MOF could achieve one-step acquisition of polymer-grade C 2 H 4 (> 99.9 %) during C 2 H 6 /C 2 H 4 and C 3 H 6 /C 2 H 4 separations. Noteworthily, for a C 3 H 6 /C 2 H 4 mixture (2/5, v / v ), high-purity C 2 H 4 (> 99.9 %) and C 3 H 6 (> 99.5 %) can be directly harvested or recovered upon desorption, with high productivities of 86.23 and 31.05 L kg −1 , respectively, surpassing many well-developed adsorbents for C 3 H 6 /C 2 H 4 separation. Theoretical calculations reveal that the nonpolar pore surface bearing accessible N and O atoms affords more hydrogen bonding interactions with C 2 H 6 and C 3 H 6 than C 2 H 4 , accounting for the adsorption affinity in the order of C 3 H 6 > C 2 H 6 > C 2 H 4 . This work may offer valuable insights into the design and construction of high-performance MOFs for one-step C 2 H 4 purification.
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
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2023
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IF 9.9
Yafei Qu,Wei Zheng,Peichen Wang,Hao Huang,Minxue Huang,Lin Hu,Hui Wang,Qianwang Chen
Electrochemical carbon dioxide reduction reaction (CO 2 RR) is an effective approach to capture CO 2 and convert it into value-added chemicals and fuels, thereby reducing excess CO 2 emissions. Recent reports have shown that copper-based catalysts exhibit excellent performance in converting CO 2 into multi-carbon compounds and hydrocarbons. However, the selectivity to the coupling products is poor. Therefore, tuning CO 2 -reduction selectivity toward C 2+ products over Cu-based catalyst is one of the most important issues in CO 2 RR. Herein, we prepare a nanosheet catalyst with interfaces of Cu 0 /Cu + . The catalyst achieves Faraday efficiency (FE) of C 2+ over 50% in a wide potential window between − 1.2 V to − 1.5 V versus reversible hydrogen electrode (vs. RHE). Moreover, the catalyst exhibits maximum FE of 44.5% and 58.9% towards C 2 H 4 and C 2+ , with a partial current density of 10.5 mA cm −2 at − 1.4 V. Density functional theory (DFT) calculations show that the interface of Cu 0 /Cu + facilitates C C coupling to form C 2+ products, while inhibits CO 2 conversion to C 1 products.
研究领域:
电化学
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催化
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材料科学
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能量转换
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DOI
PubMed
高影响因子
Journal of Environmental Sciences
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2026
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IF 6.5
Zongyao Ying,Yingjie Wang,Xiaoyan Shi,Zidi Yan,Wenmiao Li,Yulong Shan,Yunbo Yu
Pd/SSZ-39 catalyst shows high performance for NO and C 2 H 4 adsorption even after hydrothermal aging at 850 °C. • Pd 2+ ions in Pd/SSZ-39 serve as active sites for both C 2 H 4 and NO adsorption. • In the co-existence of NO and C 2 H 4 , Pd/SSZ-39 preferentially adsorb NO while also retaining the ability to C 2 H 4 adsorption. In this work, Pd/SSZ-39 zeolite catalyst (an AEI-type) was studied as a passive NO x adsorber (PNA) and hydrocarbon trap aiming for cold-start emission control in diesel vehicles. The fresh and hydrothermally aged Pd/SSZ-39 were characterized by XRD, 27 Al NMR, H 2 -TPR, NO x -TPD and DRIFTS of CO adsorption to investigate the changes of zeolite structure and Pd species. The catalytic performance of fresh and hydrothermally aged catalyst in low temperature NO and C 2 H 4 adsorption were evaluated. Moreover, systematic PNA experiments under various conditions were conducted to study the NO and C 2 H 4 adsorption, as well as oxidation of C 2 H 4 and CO on Pd/SSZ-39. Moreover, the interaction of NO with CO or C 2 H 4 were studied by in situ DRIFTS experiments. Results demonstrate that Pd 2+ ions in Pd/SSZ-39 serve as the active sits for both C 2 H 4 and NO adsorption. In the gaseous mixtures of NO and C 2 H 4 , Pd 2+ ions in Pd/SSZ-39 tend to preferentially adsorb NO rather than C 2 H 4 . Both C 2 H 4 and CO act as a reducing component which enhances the NO adsorption and shifts the NO desorption to higher temperatures. Download: Download high-res image (237KB) Download: Download full-size image
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高影响因子
Journal of Energy Chemistry
·
2026
·
IF 15.6
Xingyang Wu,Yucui Xiang,Liyong Gan,Shuaijun Wang,Zhongkai Hao,Guo Qin Xu,John Hon Kay Yip
Selective solar-driven conversion of CO 2 into C 2 hydrocarbons under aqueous conditions is a promising route toward carbon neutrality. However, C 2 selectivity in water is severely constrained because the intrinsically slow C–C coupling requires sustained electron flux to build up coupling-relevant intermediates. This flux is readily depleted by the competing hydrogen evolution reaction and rapid carrier recombination. Here, we construct an in situ S-scheme heterojunction of CuO islands on two-dimensional (2D) N-TiO 2 (CuO/N-TiO 2 ) via a one-pot solvothermal strategy. The chemically anchored CuO islands on 2D N-TiO 2 nanosheets create a compact, coherent interface that facilitates interfacial charge transfer. Compared with an ex situ assembled counterpart, the in situ heterojunction shows more efficient S-scheme charge separation. In situ characterizations and theoretical calculations reveal that dynamically redox-cycling Cu 2+ /Cu + sites are beneficial for C 2 H 4 formation, with Cu + sites favoring *CO retention and Cu 2+ sites being more favorable for the subsequent asymmetric *CO–*CHO coupling step. Consequently, the as-prepared catalyst delivers 17.5 μmol g −1 ethylene in 4 h with 94.6% selectivity and robust cycling stability. This work establishes an in situ S-scheme heterojunction with oxide islands anchored on 2D nanosheets that integrates charge management with dynamic active sites for selective aqueous CO 2 -to-C 2 H 4 photoreduction. An in situ grown CuO-islands/2D N-TiO 2 S-scheme heterojunction promotes charge separation for aqueous CO 2 -to-C 2 H 4 photoreduction without sacrificial agents. The dynamic Cu 2+ /Cu + active sites favor *CO formation, asymmetric *CO–*CHO coupling, and ethylene selectivity. Download: Download high-res image (161KB) Download: Download full-size image
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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IF 24.319
Wenjie Li,Lifen Li,Qineng Xia,Song Hong,Lijun Wang,Zhibo Yao,Tai-Sing Wu,Yun-Liang Soo,Hao Zhang,Tsz Woon Benedict Lo,Alex W. Robertson,Qingya Liu,Leiduan Hao,Zhenyu Sun
Electrochemical CO 2 reduction (ECR) to commodity chemicals offers a promising way for mitigating the greenhouse effect and driving the transition from fossil-fuel dependence to a sustainable economy. To this end, the design and development of active and robust electrocatalysts is key. Here we report for the first time that incorporation of bismuth (Bi) single atoms on defective CuO could significantly enhance the ECR reaction to C 2 H 4 by decreasing C–C coupling barriers. The overpotential for C 2 H 4 production is lowered by at least 50 mV, along with a two-fold improvement in the faradaic efficiency, reaching 60% at 400 mA cm −2 . The high performance is maintained even after 20 h of consecutive electrolysis. Control experiments along with density functional theory calculations suggest that the joint incorporation of Bi and oxygen vacancies greatly promotes CO 2 adsorption and lowers C–C coupling energy barriers, thereby improving the C 2 H 4 selectivity.
研究领域:
材料科学
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电化学
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催化
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可持续能源
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高影响因子
Catalysis Science & Technology
·
2021
·Vol. 11
·期 20
·6742-6749
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IF 6.119
Zuoyu Yan,Xiuxiu Wang,Yang Tan,Aihua Liu,Fenqiang Luo,Miaorong Zhang,Lingxing Zeng,Yan Zhang
Metals and their alloy-based electrocatalysts continue to attract considerable attention for electrochemical carbon dioxide reduction reactions (CO2RRs). In this work, cuprous oxide (Cu2O) was supported on N-doped flexible roughed graphite paper (NGP) to fabricate Cu2O/NGP self-supporting electrocatalysts for CO2RRs by electrodeposition and heat treatment. In the Cu2O/NGP electrocatalyst, NGP acted as a current collector and conducting channel, which can effectively transfer electrons from the active sites of Cu2O to NGP, and thus, enhance the catalytic performance of Cu2O/NGP for CO2RRs. The overall Faradaic efficiency of Cu2O/NGP for CO2RRs reached 96% at −0.9 V vs. reversible hydrogen electrode, of which 35% originated from yielding ethylene (C2H4), suggesting its high activity and C2H4 selectivity. Furthermore, the excellent stability of Cu2O/NGP over 10 h made it preferable as an effective electrocatalyst for CO2RRs. The good electrocatalytic performance could be attributed to the unique self-supporting structure and the synergetic effect between Cu2O and NGP.
研究领域:
材料科学
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电化学
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高影响因子
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