SEPARATION AND PURIFICATION TECHNOLOGY
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2023
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IF 8.6
Hua Shuai,Junhui Liu,Yesong Teng,Xing Liu,Lingmin Wang,Hanting Xiong,Pengxiang Wang,Jingwen Chen,Shixia Chen,Zhenyu Zhou,Shuguang Deng,Jun Wang
Energy-efficient adsorptive separation shows great potential for the one-step production of high-purity ethylene (C 2 H 4 ) from ternary C 2 hydrocarbons. However, it remains a formidable challenge to fabricate high-performance adsorbents that exhibit simultaneous high selectivity (>2) towards acetylene/ethylene (C 2 H 2 /C 2 H 4 ) and ethane/ethylene (C 2 H 6 /C 2 H 4 ). Herein, we report a pillar-layered metal–organic framework, Ni(sdba)(dabco) 0.5 (H 2 sdba = 4,4′-sulfonyldibenzoic acid; dabco = 1,4-diazabicyclo [2.2.2] octane), for preferential trapping of C 2 H 6 and C 2 H 2 over C 2 H 4 . The abundant accessible binding sites endow Ni(sdba)(dabco) 0.5 with outstanding C 2 H 2 /C 2 H 4 (2.28) and C 2 H 6 /C 2 H 4 (2.47) selectivity with high C 2 H 6 (3.15 mmol g −1 ) and C 2 H 2 (4.41 mmol g −1 ) uptake among porous materials reported for one-step C 2 H 4 purification. Dynamic breakthrough experiments demonstrated the feasibility of producing high-purity C 2 H 4 (>99.9%) from C 2 H 2 /C 2 H 6 /C 2 H 4 gas-mixtures (1/1/1 and 1/9/90, v/v/v ) in a single step. Computational simulations reveal that the aromatic-rich pore spaces, which decorated with accessible interlayer uncoordinated oxygen atoms of sulfonyl groups and alkyl functionalities, can provide multiple C-H···O, C-H···π, and C-H···H interactions for selectively recognizing C 2 H 6 and C 2 H 2 over C 2 H 4 .
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
ACS Applied Materials & Interfaces
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2025
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IF 8.2
Changjiang Liu,Hu Zang,Xin Liu,Haiyan Lu,Nan Yu,Baoyou Geng
Copper-based catalysts demonstrate distinctive multicarbon product activity in the CO2 electroreduction reaction (CO2RR); however, their low selectivity presents significant challenges for practical applications. Herein, we have developed a multilevel porous spherical Cu2O structure, wherein the mesopores are enriched with catalytic active sites and effectively stabilize Cu+, while the macropores facilitate the formation of a “gas–liquid–solid” three-phase interface, thereby creating a microenvironment with an increasing water concentration gradient from the interior to the exterior. Potential-driven phase engineering and protonation synergistically optimize the reaction pathway, facilitating a switch between CO and C2H4. At a low current density of 100 mA cm–2, the faradaic efficiency (FE) for CO reaches an impressive 96.97%. When the current density increases to 1000 mA cm–2, FEC2H4 attains 53.05%. Experiments and theoretical calculations indicate that at lower potentials, the pure Cu2O phase diminishes the adsorption of *CO intermediates, while weak protonation inhibits hydrogen evolution reactions, thereby promoting CO production. Conversely, at more negative potentials, the Cu0/Cu+ interface and strong protonation generate locally elevated concentrations of *CO and *COOH intermediates, which enhance C–C coupling and deep hydrogenation, ultimately improving selectivity toward C2+ products. This study provides novel insights into the rational design of copper-based catalysts for customizable CO2 electroreduction products.
研究领域:
材料科学
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电化学
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PubMed
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
FUEL
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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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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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IF 24.319
Honglin Li,Shoufu Cao,Hongman Sun,Yonglian Lu,Ying Zhang,Xiaoqing Lu,Jingbin Zeng,Zifeng Yan
Copper (Cu) has been proved as an efficient catalyst in carbon dioxide electrochemical reduction reaction (CO 2 RR) towards hydrocarbons, but still suffers from low selectivity and poor stability. Herein, Cu-based/CxNy catalysts were fabricated by facile pyrolysis of CuNCN in sealed quartz tubes. It is found that CuNCN pyrolyzed at 300 °C (CuNCN-300) exhibits a high C 2 H 4 Faradaic efficiency of 48.5% at 500 mA cm - 2 . However, increasing the pyrolysis temperature above 400 °C gives rise to CH 4 being the predominant product and CuNCN-500 achieves CH 4 Faradaic efficiencies of 66.3% at 300 mA cm - 2 . Combining experimental and DFT calculation results, Cu 3 N plays a crucial role in the formation of C 2 H 4 , while tri-s-triazine units in CuNCN-500 reduce the barrier of *CO hydrogenation to *CHO and retard C-C coupling on Cu surface. These findings mark the significance of precise tailoring of the synergistic effect between g-C 3 N 4 and different Cu species for achieving the desired selectivity during CO 2 RR.
研究领域:
材料科学
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电化学
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理论计算
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高影响因子
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