Advanced Energy Materials
·
2023
·Vol. 13
·期 42
·2302692
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IF 27.8
Qingyu Wang,Yida Zhang,Minxi Lin,Hengwei Wang,Yu Bai,Chengyuan Liu,Junling Lu,Qiquan Luo,Gongming Wang,Hai-Long Jiang,Tao Yao,Xusheng Zheng
Metastable structures are promising candidates for efficient catalysis owing to abundant active electronic states, strong electronic coupling with reactants, and energetic preference. Exerting the value of metastable structures while evading the difficulty in direct synthesis remains challenging. Herein, it is reported that light irradiation enables the generation and maintenance of the metastable state over copper single atoms for efficient carbon dioxide reduction. Under irradiation with light, photogenerated electrons transit to Cu-3 d orbits and initiate d -orbital rearrangement. The initial symmetric Cu 1 ─O 4 coordination converts to the metastable asymmetric structure of Cu 1 ─O 2+1 , and is reversibly restored after removing the light. The photoinduced metastable intermediate of Cu 1 ─O 2+1 promotes the Cu single-atom catalyst to deliver an ethylene yield rate of 60.4 µmol g cat. −1 h −1 . Mechanistic studies reveal that Cu 1 ─O 2+1 possesses stronger adsorption capability for reactants and intermediates. The reaction energy barrier over Cu 1 ─O 2+1 also shows an obvious decline compared to that over Cu 1 ─O 4 .
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ACS Applied Nano Materials
·
2023
·
IF 5.9
Xiaoqian Peng,Jing Zhang,Jinqiang Sun,Xiaochan Liu,Xinfu Zhao,Shimo Yu,Zhipeng Yuan,Sijia Liu,Xibin Yi
One of the most promising methods for capturing carbon dioxide (CO2) is solid physical adsorption, which is an efficient and simple technique. The key to effective CO2 capture is the development of high-performance solid adsorbents with excellent CO2 adsorption capacity, CO2/N2 selectivity, and rapid adsorption/desorption kinetics. In this paper, a Mg-MOF-74/sodium alginate composite aerogel was prepared by loading Mg-MOF-74 on sodium alginate sheets followed by directional freeze-drying. The composite aerogel exhibited a hierarchical porous structure, in which sodium alginate provided an open mesoporous/macroporous structure that promoted diffusion and contact with the active center of CO2. The Mg-MOF-74 micropores/mesopores promoted the strong interaction between CO2 and the adsorbent in the micropore and rapid mass transfer of CO2 to the adsorbent through the mesopores. The experimental data showed that MSA-6 achieved CO2 adsorption of 2.461 mmol·g–1 at 298 K. Furthermore, the CO2/N2 adsorption selectivity of MSA-6 reached 35.108, indicating its strong CO2 selective adsorption potential.
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2023
·
IF 6.1
Wei Rong,Meili Ding,Pan Ma,Suyu Kong,Jianfeng Yao
Accumulation of atmospheric CO 2 poses a serious threat to the global environment, but there is still a lack of effective CO 2 catalytic conversion under mild conditions. Herein, multifunctional ZnO/N-doped porous carbon materials, ZNPC-X, were fabricated by pyrolysis of available pine pollen with melamine and zinc chloride . The optimized ZNPC-600 produced at 600 °C can work as an efficient photothermal catalyst towards CO 2 cycloaddition conversion with a high catalytic yield of 99% under mild conditions (0.3 W/cm 2 , 1 bar). Moreover, ZNPC-600 shows excellent recyclability after ten cycles and desirable performance even under simulated flue gas and after moisture treatment. Absorption spectra and time-dependent infrared images unveil that the intrinsically broad light absorption and high photothermal conversion efficiency are the major reasons for the high activity of ZNPC-600. Besides, photogenerated electrons can be transferred to CO 2 and activate it, while photogenerated holes can be used as Lewis acid to facilitate the ring opening of epoxides. In addition, the hierarchical pore structure and the synergy between ZnO and pyridine N also play a role in the mass transfer and activation of epoxides and CO 2 , respectively. This work provides a low-cost and facile solution to obtain catalysts derived from biomass for promoting CO 2 conversion.
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Molecular Catalysis
·
2021
·
IF 5.062
Rui Tang,Niamat Ullah,Yajun Hui,Xin Li,Zhenhua Li
Carbon dioxide hydrogenation for value-added chemicals has been regarded as a promising way for CO 2 utilization. This paper describes the preparation of Ni/CeO 2 catalysts derived from Ce-MOF precursor by impregnation or one-pot method and their application in carbon dioxide methanation. Various techniques were employed to characterize the prepared catalysts, including N 2 adsorption–desorption, X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (SEM), H 2 -temperature programmed reduction (H 2 -TPR), H 2 -temperature programmed desorption (H 2 -TPD) and CO 2 -temperature programmed desorption (CO 2 -TPD). The results showed that compared with commercial CeO 2 and CeO 2 prepared by precipitation, CeO 2 derived from Ce-MOF exhibited more oxygen vacancies and lower temperature reducibility, making it more beneficial for the adsorption and activation of CO 2 . Consequently, nickel supported on rod-shaped CeO 2 derived from Ce-MOF exhibited higher CO 2 conversion and methane selectivity at low temperatures. Furthermore, the Ni/CeO 2 −M-1 catalysts prepared by one-pot method showed superior activity since nickel could be partially incorporated into ceria lattice, leading to the formation of Ce 1-x Ni x O 2-y solid solutions and oxygen vacancies. The effect of nickel loading on the properties of the catalysts by one-pot method was also investigated, and the optimum Ni loading was 15 wt.% owing to the maximum number of oxygen vacancies being reached.
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CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Jun Mou,Xingqi Fan,Fei Liu,Xiaodan Wang,Tianxiang Zhao,Peng Chen,Ziwei Li,Chunliang Yang,Jianxin Cao
The direct conversion of CO 2 hydrogenation to lower olefins via methanol as an intermediate is of great significance, but challenges still remain. Herein, we present a binary Mn 2 O 3 -ZnO oxide, which is responsible for catalytic hydrogenation of CO 2 to methanol. After combination of Mn 2 O 3 -ZnO and SAPO-34 molecular sieve, the catalytic reaction displays a markable increase. CO 2 adsorption by alkaline nature, followed by oxygen vacancy activation and synergistic hydrogenation over the binary Mn 2 O 3 -ZnO oxide are the prerequisites for the tandem reaction. However, the tandem spacing between oxide and molecular sieve plays a crucial role, because the suitable intimacy can induce enhanced methanol formation as intermediate via tandem dynamics effect, causing an apparent limitation for reverse water gas shift reaction at high temperature. The optimum mass ratio of 3:1 for two phases demonstrates that more components of binary oxide are needed to improve the rate of CO 2 hydrogenation to methanol, aiming to balance the two-step tandem reaction. Finally, under conditions of 380 ℃, 3 MPa and 3600 mL/g cat /h, 20%Mn 2 O 3 -ZnO/SAPO-34 tandem catalyst is obtained by physical ball milling after 15 min, with excellent stability, sulfur tolerance and catalytic performance with CO 2 conversion at almost 30%, lower olefins selectivity of 80.2% (propylene/ethylene = 5.6:1), and single-pass yield of 10.7%.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Mingpu Kou,Wei Liu,Yongye Wang,Jindi Huang,Yanli Chen,Ying Zhou,Yi Chen,Minzhi Ma,Kai Lei,Haiquan Xie,Po Keung Wong,Liqun Ye
The application of covalent organic framework (COF) for photocatalytic CO 2 conversion has received more and more attention. However, it is still a challenge for photocatalytic conversion of CO 2 with atmosphere concentration to high added value hydrocarbons products (C x H y ) such as CH 4 and C 2 H 4 . Here, integrating the advantages of micropore structure and single atom catalysis, we introduced single- atom MoN 2 sites into COF to construct Mo-COF materials. The aberration-COrrected high-angle annular dark-field scanning transmission electron microscopy (HAADF- STEM) confirms that Mo single atom on COF. Mo-COF can reduce CO 2 to C x H y under visible light with a selectivity of 42.92 % and C 2 H 4 product was found for the the first time. In-situ fourier transform infrared spectrometer (In situ FT-IR) and theoretical calculation showed that the introduction of single-atom MoN 2 sites is the key to improving the catalysis performance. It also provides a new idea for converting CO 2 into high added value C x H y products.
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REACTIVE & FUNCTIONAL POLYMERS
·
2021
·
IF 3.975
Hui Wang,Yunxia Ni,Zhiyue Dong,Qiang Zhao
Interface compatibility is crucial to performance and robustness of nanocomposite membranes for molecular separation. In this work, a covalent crosslinking method was exploited to fabricate polydimethylsiloxane/metal-organic-frameworks (PDMS/MOFs) mixed matrix membranes with improved interfacial compatibility. Zirconium MOF particles (UiO-66-NH 2 ) were grafted with methoxysilane groups, which further formed covalent crosslinks with silanol terminated PDMS matrix. The strengthened interfacial compatibility prevented sedimentation and aggregation of MOF particles in PDMS precursor solution during the solvent evaporation process, thus the composites showed good membrane formation ability at high MOFs loading (60 wt%). Tensile strength of the hybrid membrane is 2.8 times improved while retaining good flexibility. Moreover, the CO 2 /N 2 selectivity and CO 2 permeability of the PDMS composite membrane incorporated with 40 wt% UiO-66-MS particles are improved by 1.3 times and 0.7 times, respectively.
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REACTIVE & FUNCTIONAL POLYMERS
·
2021
·
IF 3.975
Yunfan Zhang,Jialin Liu,Jingbo Zhao,Zhiyuan Zhang
A new and simple method was established to prepare polyamides with a chelating feature through Michael addition and polycondensation . A piperazine-diester monomer , that is, N,N´-bis(methyl propanoate) piperazine (BMPZ), was synthesized through a Michael addition of piperazine and methyl acrylate . Three polyamides containing piperazine rings (PIP-PAs) were synthesized via melt polycondensation from BMPZ and different diamines. PIP-PAs were modified by chelating Co 2+ , and several PIP-PA-Co 2+ complexes were obtained. The structure of BMPZ and PIP-PAs was characterized by FT-IR and 1 H NMR spectra. DSC and wide angle X-ray diffraction verified the crystallizable feature of PIP-PAs. They possessed T m from 81 °C to 171 °C, tensile strength up to 31 MPa, and good toughness. Chelating PIP-PAs with Co 2+ was accompanied by color change and the loss of crystallization. The effect of chelation on T g , tensile strength, and Young's modulus was investigated. Polyamide complexes with good mechanical property and solvatochromic feature were synthesized successfully.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Xiangdong Kong,Jingwen Ke,Zhiqiang Wang,Yan Liu,Yibo Wang,Weiran Zhou,Zhengwu Yang,Wensheng Yan,Zhigang Geng,Jie Zeng
A typical mode of CO 2 activation is that d electrons at the d orbital of transition metals transfer to the unoccupied π * orbital of CO 2 . Thus the exploration of the relationship between d -electron behaviors and CO 2 activation is of great importance. Herein, we demonstrate that high-spin state of 3 d electrons in Co 2+ facilitated the activation of CO 2 over Co-salophen-X (X represents to Cl, Br, or I). Among these catalysts, Co-salophen-Br exhibited the highest Faradaic efficiency for CO. Notably, the Faradaic efficiency for CO over Co-salophen-Br reached 98.5 % at −0.70 V versus reversible hydrogen electrode, which was 1.5 and 1.2 times as high as those over Co-salophen-Cl (64.8 %) and Co-salophen-I (81.8 %), respectively. Density functional theory calculations revealed that high-spin state of Co sites decreased the reaction energy barrier for the formation of CO. Based on the analysis of electronic state, the ratio of high-spin state was 65.6 % for Co-salophen-Br, which was the highest among the three Co-based molecules. The Co sites with high-spin state promoted the electron transfer from high-energy 3 d orbital (3 d z2 and 3 d x2-y2 ) of Co to the unoccupied π * orbital of CO 2 , improving catalytic performance.
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Journal of CO2 Utilization
·
2021
·
IF 7.132
Ziyi Zhao,Xiaotong Li,Jianghao Wang,Xiangzhou Lv,Hao Bin Wu
Electrochemical reduction of carbon dioxide to value-added fuels offers a promising method to solve increasingly serious environmental problems and alleviate energy crisis. Herein, we report a facile method by coating Cu electrode with CeO 2 nanoparticles to largely enhance the C 2+ products selectivity during CO 2 electroreduction. The Faradaic efficiency of C 2+ products for optimal CeO 2 -coated Cu electrode reached a high value of 61 % at -1.05 V vs RHE, and exhibited good stability for over 9 h of CO 2 electrolysis. The CeO 2 nanoparticles were found to induce oxidative corrosion of the Cu foil, leading to a CuO x layer in contact with the CeO 2 nanoparticles. The interface between CeO 2 nanoparticles and oxide-derived Cu might be attributed to the enhanced catalytic activity for C 2+ products by promoting the C C coupling process.
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JOURNAL OF MATERIALS SCIENCE
·
2021
·Vol. 56
·期 28
·15653-15666
·
IF 4.22
Zhang Nan,Zhang Yaoming,Duan Chunjian,Li Song,Yang Zenghui,Zhang Xinrui,Wang Tingmei,Wang Qihua
Traditional “top-down” methods for graphene preparation, like micromechanical cleavage and ultrasound methods, usually cannot preserve both efficiency and quality simultaneously. Herein, we provide an environmental-friendly graphene exfoliating method with high efficiency and high quality that combines the microfluidization process (liquid phase) and supercritical carbon dioxide process (gas phase), namely the dual-phase exfoliating (DPE) method. The combination of effective tangential force (shearing force) and normal force (push and pull), which are originally from microfluidization and supercritical carbon dioxide process, respectively, maximizes the exfoliating efficiency. The DPE method offers a high yield of up to 70.25% for graphene preparation (941.04 g per day theoretically), while the graphene sheets could remain single or a few layers (> 80%) and around micron size. By molecular dynamic simulations, it is theoretically proved that carbon dioxide can intercalate between graphite layers and expand the interlayer spacing under supercritical conditions. This DPE method, by combining the advantages of different phase processes, provides an ideal process design perspective for large-scale preparation of other 2D materials.
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Journal of CO2 Utilization
·
2021
·
IF 7.132
Jinsong Shi,Hongmin Cui,Jianguo Xu,Nanfu Yan,Chao Zhang,Shengyong You
Porous carbon with specifically designed structure as CO 2 adsorbent is a very attractive and interesting research topic. In this study, we presented the synthesis and CO 2 adsorption of flower shaped porous carbons. Flower-like hydrochar derived from the hydrothermal reaction of glucose, cobalt sulfate, and hexamethylenetetramine was used as the precursor, which was converted to carbon flower during CO 2 activation. The flowers had hierarchically macro-meso-microporous structure. Interspaces and voids were formed by assembly of the petals, and the petals were distributed with pores of different scales. The formation mechanism of, and influences of various synthesis parameters on the flower shape were studied and analyzed. The carbon flowers exhibited surface area of 422−691 m 2 /g, and very high nitrogen content of 9.31–11.91 wt%. CO 2 adsorption performances of the carbon flowers were also studied. Influences of the textural properties and doped nitrogen on the adsorption performances were investigated. The experiment results demonstrated that nitrogen doping showed positive effects on CO 2 uptake at 1 bar, and had strong influence on the CO 2 /N 2 selectivity.
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