SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Jialang Hu,Yan Zhang,Mingyuan Jiang,Chao Xiong,Shenwei Chen,Jin Li,Xu Li,Ziyuan Zhu,Peng Hu,Hongbing Ji
Effective separation of acetylene/ethylene (C 2 H 2 /C 2 H 4 ) mixtures by adsorption is a challenging but green method given their similar molecular characters. An increasing number of metal-organic frameworks (MOFs) have addressed the diffusion-related challenges to achieve the separation, yet almost all of them just focus on diffusion rates and disregard the geometrical arrangement of adsorbed molecules which exerts important effects in boosting the diffusion behaviors. Herein, we now present a paradigm using an ultramicroporous zinc-MOF (Zn-MOF, referred to as 1 ) with assessable size of 3.4 × 3.3 Å 2 , as demonstrated by single-crystal and theoretical analysis, which realizes the effective separation of C 2 H 2 from its competitors. Static adsorption isotherms indicate that 1 possesses higher C 2 H 2 uptake of 28.4 cm 3 g −1 at 298 K and 0.1 bar, achieving a high IAST selectivity of 265 among the benchmark MOFs. Theoretical calculations reveal that C 2 H 2 molecules are grasped through multiple binding interactions and adsorbed in the pore surface rather than the center of the pore, thus forming C 2 H 2 tetramer through connecting four C 2 H 2 motifs. Further, time-dependent kinetic tests coupled with molecular dynamics confirm the faster diffusion behavior for C 2 H 2 , mainly attributing to unimpeded diffusion channel. Column breakthrough tests demonstrate that 1 can easily accomplish exclusive separation of C 2 H 2 from various binary ethane dehydrogenation (EDH) and senary non-oxidative coupling of methane (non-OCM) byproducts. Specially, structurally stable 1 can be readily synthesized utilizing inexpensive raw materials, yielding the cost of only $614 per kilogram. Accordingly, this work proposes a novel strategy of wall-trapped C 2 H 2 tetramer in MOF that can effectively promote the kinetic behavior through available diffusion channel, expecting to offer a new perspective and provide guidance for future research.
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 SOLID STATE CHEMISTRY
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2021
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IF 3.498
Di-Ming Chen,Yin-Ping Zheng,Shao-Ming Fang
The selective separation of C 2 H 2 from C 2 H 4 is a very important process for downstream industrial production, and porous metal-organic frameworks (MOFs) have shown great potential for such an application due to their tunable pore surroundings and adjustable building blocks. In this study, a new microporous MOF formulated as {(Et 2 NH 2 )[In(TBOT)(2,3-FDA)](DEF)(H 2 O) 2 } n ( 1 , H 3 TBOT = 4,4′,4’’-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(oxy))tris(methylene))tribenzoic acid, 2,3-HFDA = 2,3-difluorobenzoic acid and DEF = N , N -diethylformamide) with 2-fold interpenetrated network and 1D fluorine-decorated pores has been prepared via using an acid-acid mixed-ligand strategy. The activated complex 1 (named as 1a ) demonstrates apparently higher C 2 H 2 uptake than C 2 H 4 around room temperature , resulting in its relative high C 2 H 2 /C 2 H 4 (v:v = 1:99) IAST (Ideal Adsorbed Solution Theory) selectivity of 10.3 at 298 K and 1 bar. Furthermore, the GCMC (grand canonical Monte Carlo) simulation results indicate that the 2,3-FDA moieties serve as preferential binding sites for C 2 H 2 via the multipoint F 2 ⋯H–C C–H⋯F 2 interactions, implying the feasibility of the mixed-ligand approach for building porous MOFs with the targeted applications.
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
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
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2023
·Vol. 120
·期 44
·e2307320120
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IF 11.1
Yangyang Yu,Ye He,Ping Yan,Shengyao Wang,Fan Dong
The selective photocatalytic conversion of CO2 and H2O to high value-added C2H4 remains a great challenge, mainly attributed to the difficulties in C–C coupling of reaction intermediates and desorption of C2H4* intermediates from the catalyst surface. These two key issues can be simultaneously overcome by alloying Ag with Cu which gives enhanced activity to both reactions. Herein, we developed a facile stepwise photodeposition strategy to load Cu–Ag alloy sub-nanoclusters (ASNCs) on TiO2 for CO2 photoreduction to produce C2H4. The optimized catalyst exhibits a record-high C2H4 formation rate (1110.6 ± 82.5 μmol g−1 h−1) with selectivity of 49.1 ± 1.9%, which is an order-of-magnitude enhancement relative to current work for C2H4 photosynthesis. The in situ FT-IR spectra combined with DFT calculations reveal the synergistic effect of Cu and Ag in Cu–Ag ASNCs, which enable an excellent C–C coupling capability like Ag and promoted C2H4* desorption property like Cu, thus advancing the selective and efficient production of C2H4. The present work provides a deeper understanding on cluster chemistry and C–C coupling mechanism for CO2 reduction on ASNCs and develops a feasible strategy for photoreduction CO2 to C2 fuels or industrial feedstocks.
研究领域:
化学
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材料科学
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环境科学
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DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2018
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IF 3.927
Houxiao Wu,Yongwei Chen,Daofei Lv,Renfeng Shi,Yang Chen,Zhong Li,Qibin Xia
The purification of ethylene (C 2 H 4 ) from the cracking gas ethane/ethylene mixture (1:15, v / v ) is a typical energy-intensive process in the chemical industry. As an alternative, adsorptive separation with much lower energy consumption and operational cost has attracted escalating attention. In this work, we reported an interesting C 2 H 6 -trapping adsorbent, In-soc-MOF-1, an indium-based metal-organic framework exhibiting the preferential adsorption of C 2 H 6 over C 2 H 4 . Single-component adsorption isotherms showed that the C 2 H 6 adsorption capacities were higher than those of C 2 H 4 under measured temperatures (288, 298 and 308 K). For example, the uptakes of C 2 H 6 and C 2 H 4 were 4.04 and 3.72 mmol/g at 298 K and 100 kPa, respectively. The calculated IAST selectivity of C 2 H 6 /C 2 H 4 (1:15) on In-soc-MOF-1 was in the range of 1.4–4.8. Moreover, the dynamic separation performance of In-soc-MOF-1 toward the C 2 H 6 /C 2 H 4 binary mixture was evaluated by the breakthrough experiments, the result of which suggests that In-soc-MOF-1 could achieve efficient separation by trapping the impurity C 2 H 6 molecules out of the C 2 H 6 /C 2 H 4 binary mixture. Notably, In-soc-MOF-1 not only showed good water and moisture stability but also exhibited excellent recyclability, where negligible decrease in C 2 H 6 adsorption capacity was observed during five cycles of adsorption-desorption tests. These properties suggest that In-soc-MOF-1, as a C 2 H 6 -trapping adsorbent, could be considered as a potential candidate in the practical application of separating the cracking gas mixture.
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
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2023
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IF 9.9
Zhixiu Yang,Xiu Wen,Xiaoxuan Guo,Yong Chen,Ruiping Wei,Lijing Gao,Xiaomei Pan,Jin Zhang,Guomin Xiao
The electrochemical CO 2 reduction to specific multi-carbon product on copper-based catalysts is subjected to low activity and poor selectivity . Herein, catalyst structure, morphology, and chemical component are systematically studied for bolstering the activity and selectivity of as-prepared catalyzers in this study. Dendritic fibrous nano-silica spheres favor the loading of active species and the transport of reactant from the central radial channel. Cu/DFNS with high dispersion active sites are fabricated through urea-assisted precipitation way. The coexistence of Cu(I)/Cu(II) induces a close combination of Cu active sites and CO 2 on the Cu/DFNS interface, promoting the CO 2 activation and C C coupling. The Cu–O–Si interface (Cu phyllosilicate) can improve CO 2 and CO attachment. Cu/DFNS show the utmost Faradaic efficiency of C 2 H 4 with a value of 53.04% at −1.2 V vs. RHE. And more importantly, in-situ ATR-SEIRAS reveals that the C C coupling is boosted for effectively producing C 2 H 4 as a consequence of the existence of *CO L , *COOH, and *COH intermediates. The mechanism reaction path of Cu/DFNS is inferred to be *CO 2 → *COOH → *CO → *CO*COH → C 2 H 4 . Our findings will be helpful to gain insight into the links between morphology, texture, chemical component of catalyzers, and electrochemical reduction of CO 2 , providing valuable guidance in the design of more efficient catalysts.
研究领域:
材料科学
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电化学
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催化反应
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DOI
PubMed
高影响因子
APPLIED CATALYSIS A-GENERAL
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2023
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IF 5.5
Guodong Sun,Yanan Cao,Deqing Li,Mingzhen Hu,Xinhu Liang,Zhe Wang,Zengjian Cai,Fengyi Shen,Bozhen Chen,Kebin Zhou
Electrochemical reduction of CO 2 to multi-carbon products is very attractive yet particularly challenging due to the low efficiency of C-C coupling over currently used electrocatalysts. In this work, we report a dual-atom catalyst (Cu 2 /NC) capable of selectively promoting electro-reduction of CO 2 to C 2 H 4 . The Faradaic efficiency of CO 2 -to-C 2 H 4 over the Cu 2 /NC is up to ∼34.9% with a current density of 33.6 mA·cm −2 . By contrast, its Cu single-atom counterpart only generates CO without forming C 2 H 4 . The density functional theory (DFT) calculations reveal that the Cu-Cu sites largely promote the adsorption of *CO and reduce the energy barrier of C-C coupling between the adsorbed *CO relative to that of the single Cu sites, which accounts for the high C 2 H 4 selectivity of the Cu 2 /NC.
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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理论化学
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DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
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2024
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IF 8.4
Hui Wang,Yutao Liu,Yongheng Ren,Siyuan Peng,Jiayou Liao,Jinping Li,Libo Li
Membrane technology is a promising candidate for ethylene/ethane (C 2 H 4 /C 2 H 6 ) separation, but the separation factor and long-term stability of commercially available polymer membranes remain still insufficient to meet industrial requirements. Incorporating facilitated metal-ion carriers or unsaturated metal sites of fillers into polymers shows exceptional C 2 H 4 /C 2 H 6 separation efficiency due to the intensified olefin-favorable sorption . However, their separation performance usually dropped within a few hours due to the inactivation of the facilitated transport carrier or poisoning of unsaturated sites in presence of water vapor . Herein, we adopt a facile and effective method to prepare long-term stable Silicalite-1@Ag (S-1@Ag) mixed matrix membranes (MMM) by in-situ embedding the vulnerable carrier Ag + into the pores of the hydrophobic zeolite to protect the Ag + from deactivation. The 12 wt% S-1@Ag filler uniformly dispersing within the commercial 6FDA-DAM exhibits superior separation performance that surpasses the 2013 upper bound in terms of C 2 H 4 permeability of 29.74 barrer and C 2 H 4 /C 2 H 6 selectivity up to 7.66 for equimolar mixed gas. Furthermore, the hydrophobicity nature and framework shielding towards Ag + of S-1 guarantees the excellent almost 2-months stable separation of C 2 H 4 /C 2 H 6 by S-1@Ag MMMs under the high relative humidity conditions, demonstrating its potential for industrial applications.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2024
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IF 3.9
Lixiao Zheng,Huayong Yang,Min Zhang,Zhongjie Guan,Qiuye Li,Jianjun Yang
Amorphous photocatalysts are characterized by numerous grain boundaries and abundant unsaturated sites, which enhance reaction efficiency from both kinetic and thermodynamic perspectives. However, amorphization strategies have rarely been used for photocatalytic CO2 reduction. Doping copper onto a metal–organic framework (MOF) surface can regulate the electronic structure of photocatalysts, promote electron transfer from the MOF to Cu, and improve the separation efficiency of electron-hole pairs. In this study, an amorphous photocatalyst MOFw-p/Cu containing highly dispersed Cu (0, I, II) sites was designed and synthesized by introducing a regulator and in situ copper species during the nucleation process of MOF (UiO-66-NH2). Various characterizations confirmed that the Cu species were anchored to the organometallic skeleton of the surface amorphization MOF structure. The synergistic effect of Cu doping and surface amorphization in MOFw-p/Cu can significantly enhance the CO and CH4 yields while promoting the formation of the multicarbon product C2H4. The approach holds promise for developing novel, highly efficient MOFs as photocatalysts for CO2 photoreduction, enabling the production of high-value-added C2 products.
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
CHEMISTRY-A EUROPEAN JOURNAL
·
2019
·Vol. 25
·期 38
·9045-9051
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IF 5.16
Lingchang Jiang,Pengyuan Wang,Meiping Li,Panpan Zhang,Jialu Li,Jia Liu,Yanhang Ma,Hao Ren,Guangshan Zhu
Graphical Lapping it up : A thermally and chemically stable, crystalline polyimide porous organic framework, was constructed by imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride with triangular 1,3,5-tris(4-aminophenyl)benzene. This material is capable of selective adsorption of C 2 H 2 over C 2 H 4 and CO 2 over N 2 (see figure). Utilization of porous materials for gas capture and separation is a hot research topic. Removal of acetylene (C 2 H 2 ) from ethylene (C 2 H 4 ) is important in the oil refining and petrochemical industries, since C 2 H 2 impurities deactivate the catalysts and terminate the polymerization of C 2 H 4 . Carbon dioxide (CO 2 ) emission from power plants contributes to global climate change and threatens the survival of life on this planet. Herein, 2D crystalline polyimide porous organic framework PAF-120, which was constructed by imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride and triangular 1,3,5-tris(4-aminophenyl)benzene, showed significant thermal and chemical stability. Low-pressure gas adsorption isotherms revealed that PAF-120 exhibits good selective adsorption of C 2 H 2 over C 2 H 4 and CO 2 over N 2 . At 298 K and 1 bar, its C 2 H 2 and CO 2 selectivities were predicted to be 4.1 and 68.7, respectively. More importantly, PAF-120 exhibits the highest selectivity for C 2 H 2 /C 2 H 4 separation among porous organic frameworks. Thus PAF-120 could be a suitable candidate for selective separation of C 2 H 2 over C 2 H 4 and CO 2 over N 2 .
研究领域:
材料科学
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化学工程
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DOI
PubMed
高影响因子
FUEL
·
2023
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IF 7.4
Jing Li,Tingshan Chan,Chuanyong Jing,Jin Wang
Selective conversion of CO 2 to fuels and chemicals has been considered one of the key challenges in the photocatalytic CO 2 reduction reaction. The multi-electron reduction reaction requires the design of photocatalysts that can adsorb CO 2 and transfer electrons. Herein, Cu single atoms are confined in a conjugated microporous polymer (CMP) to construct Cu n @CMP photocatalyst for CO 2 reduction to produce C 2 H 4 and CH 4 . By adjusting Cu loading, Cu 0.012 @CMP exhibited a high performance with production yields of 236.81 μmol·g −1 ·h −1 for C 2 H 4 , and 78.2 % selectivity for C 2 H 4 formation. DFT calculations displayed the band structure and confirmed Cu–N together with characterization. The in situ DRIFTS revealed *CH 2 and *C 2 H 4 as key reaction intermediates to form CH 4 and C 2 H 4 , respectively. The synergy effect in Cu single-atoms and CMP contributed greatly to C–C coupling and interfacial charge transfer, thus achieving excellent activity for conversion of CO 2 to C 1 /C 2 . This work highlights the potential for constructing Cu single atoms on CMP to produce highly selective C 2 H 4 .
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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高影响因子
NEW JOURNAL OF CHEMISTRY
·
2025
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IF 2.5
junhai Wang,ruoxuan Peng,Yuan-Hao Zhu,changjun You,yuan Yin,boyi Yang,yitao Si,Jiancheng Zhou
Photothermal catalytic conversion of CO2 with H2O has exhibited improved performance in solar-to-chemical (STC) energy conversion efficiency. However, the limited rate of photocatalytic half reactions has generally hindered the full exploitation of solar energy. To address this issue, we developed a CeO2/WO3 catalyst to facilitate the photoconversion process. Under concentrated light irradiation, the energy conversion efficiency of STC was increased to 0.356 ‰, which is 27.9 times higher that under non-concentrated light irradiation. The product amount of C2H4 increased from 4.36 µmol·g-1·h-1 to 124.21 µmol·g-1·h-1, representing a 27.5-fold increase. This success could be attributed to the photo-thermal synergistic effects which provided the photoexcited carriers with additional kinetic energy. Besides, the abundance of active sites at the heterojunction interfaces shortened the charge transfer distance and facilitated C-C coupling. This research contributes to the efficient and environmentally friendly use of solar energy to drive CO2 conversion with photothermal catalytic systems, and highlights the critical importance of heterojunction interfaces during the photocatalytic reactions.
研究领域:
催化化学
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能源科学
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环境科学
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高影响因子
Journal of Materials Chemistry A
·
2022
·Vol. 10
·期 25
·13333-13344
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IF 14.511
Xiaoqian Li,Dechao Wang,Zhongjie He,Fangfang Su,Jing Zhang,Yudeng Wang,Yangyang Xin,Hongni Wang,Dongdong Yao,Mingtao Li,Yaping Zheng
The introduction of ionic liquids crystals (ILCs) into porous liquids (PLs) might be an effective way to overcome the problems associated with their processability, such as leakage, packaging, transportation, and long-term stability. Herein, a generalizable strategy to construct stimuli-responsive porous ionic liquids (SRPILs) based on the self-assembly of responsive ILCs and metal–organic frameworks (MOFs) has been demonstrated. The unique rapid reversible transition behaviors of the SRPILs induced by shearing and heating stimuli are verified. Furthermore, the SRPILs exhibited an approximately 3-fold increase in adsorption capacity for CO2 and C2H4 compared with that of the neat ILC solvent, confirming that the accessible porosity was retained in the SRPILs. Remarkably, the stimuli-responsiveness of the SRPILs can be demonstrated through changes in their phase, porosity, gas adsorption, and separation. Benefiting from their stimuli-responsive nature, SRPILs can be regarded as “smart porous liquids”, undoubtedly providing enormous inspiration for the development of new applications, including but not limited to gas capture/separation, sensing, catalysis, and electrochemical applications.
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
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