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    Home > Newsroom > Research Progress

    Scientists Discover Novel Strategy for Selectivity Tuning in Alcohol Synthesis by Crystal Phase Engineering

    A research team at Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences reported for the first time an efficient FeZn-based catalyst for methanol synthesis via CO2 hydrogenation and by crystal structure, achieving high methanol selectivity of 84.5%.The research results were published in the latest issue of Chem.


    　　A research team led by Prof. GAO Peng and Prof. LI Shenggang at Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences developed an efficient FeZn-based catalyst for methanol synthesis via CO2 hydrogenation. After investigating the crystal structure engineering of FeZn catalysts, the research team reported for the first time that ZnFe2O4 spinel enables high methanol selectivity of 84.5% in CO2 hydrogenation.
    　　The research results were published in the latest issue of Chem.
    　　The catalytic conversion of CO2 into alcohols using low-cost green hydrogen is a promising solution for mitigating CO2 emissions. Substantial progress has been made in developing efficient CO2-to-methanol catalysts and revealing the reaction mechanisms, in which highly selective CO2 hydrogenation into alcohols remains a great challenge, due to the difficulty in controlling the C-C coupling steps.
    　　Noble metal-based catalysts were reported to exhibit high ethanol selectivity in CO2 hydrogenation to higher alcohols containing two or more carbon atoms (C2+OH). The research team investigated how crystal structure engineering of FeZn catalysts transformed selective product formation from methanol to C2+OH, realizing unprecedented higher alcohol synthesis (HAS) performance from CO2 hydrogenation.
    　　Researchers first synthesized the single-phase crystal structure of ZnFe2O4 spinel. The ZnFe2O4 oxide sample was activated in situ prior to the CO2 hydrogenation reaction.
    　　The experimental observation showed that more than 97% of the reaction products consisted of methanol and ZnFe2O4 catalyst exhibited a high CH3OH selectivity and CO2 conversion. ZnO and Fe2O3 oxides were synthesized and tested for comparison study, which shown a much lower CO2 conversion and CH3OH selectivity.
    　　The results indicated the ZnFe2O4 spinel phase enabled high methanol selectivity during CO2 hydrogenation. The experimental analysis suggested the oxygen vacancy on the surface of ZnFe2O4 spinel is the active site for CO2 and H2 activation.
    　　It was also found that spinel ZnFe2O4 plays a vital role in the formation of oxygenates from CO2 hydrogenation, whereas the formation of the Fe5C2 phase facilitates both carbon chain growth and the insertion of C1 oxygen-containing intermediates to yield C2+OH after further hydrogenation, which greatly increases the selectivity of C2+OH in addition to olefins.
    　　Moreover, introducing Fe5C2 phase to the formation of the ZnFe2O4/Fe5C2 interface greatly promotes C2+OH selectivity in oxygenates to 98.2%, giving a very high C2+OH productivity and an unprecedented C3+OH yield of 5.3%, which surpass the current reported maximum C3+OH yield of 2.1%.
    　　Theoretical calculations further revealed the role of the ZnFe2O4/Fe5C2 interface in the C-C coupling. The ZnFe2O4/Fe5C2 interface drives selective transformation to C2+OH by promoting the facile migration of alkyl species to the interface and coupling with CHO* species, which contribute to the breaking of the Anderson-Schulz-Flory(ASF) distribution and result in the much lower methanol selectivity than expected.
    　　This work demonstrates a new strategy for selectivity tuning in alcohol synthesis by crystal structure engineering.
    　　Reaction networks for CO2 hydrogenation to methanol over the ZnFe2O4 and CO2 to C2+OH over the ZnFe2O4/Fe5C2 interface (Image by SARI) 
    　　

    2024-04-17 more+

    Researcher Propose Solvent Effects on Metal-free Covalent Organic Frameworks in Oxygen Reduction Reaction

    A research group at Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences, represents the first investigation into the solvent effect on COFs for catalyzing the oxygen reduction reaction (ORR). They found all COFs synthesized with different nitrogen atoms exhibited good crystallinity and high surface areas, but displayed different binding abilities towards water molecules.This work was published in Angew. Chem. In. Ed.


    　　Covalent organic frameworks (COFs) are crystalline structures composed of conjugated organic molecules, forming two-dimensional or three-dimensional frameworks.
    　　Currently, most efforts in designing COFs catalysts focus on altering the types of monomers and adjusting the framework's charge to achieve highly efficient catalysts. However, these efforts often overlook the impact of water molecules binding to nitrogen atoms within the COFs during the catalytic process, which can significantly affect the catalyst's performance.
    　　Recently, a research group led by prof. ZENG Gaofeng and XU Qing at Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences, represents the first investigation into the solvent effect on COFs for catalyzing the oxygen reduction reaction (ORR). They found all COFs synthesized with different nitrogen atoms exhibited good crystallinity and high surface areas, but displayed different binding abilities towards water molecules.
    　　This work was published in Angew. Chem. In. Ed.
    　　Researcher synthesized three COFs composed of different N kinds including imine, pyridine, and phenazine N. The interaction between the N atoms and H2O resulted in modifying electronic states and corresponding catalytic performance for the COFs. The COFs with pyridine N achieved higher catalytic activity compared to those COFs based on imine N and phenazine N sites.
    　　The theoretical calculation later revealed that the stronger binding ability of *OOH intermediates to the carbon atoms near the pyridine N sites may contribute to its higher activity.
    　　This work provides valuable insights into the significance of putting solvent effects on COFs in electrocatalytic systems design offering a new approach for their design and enhancement of electrocatalytic performance.
    　　

    2024-04-08 more+

    Researchers Develop an Adaptive NOMA-based Spectrum Sensing for Next Generation of IoT Networks

    An international collaborative research team led by the Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences proposed an innovative NOMA-based spectrum sensing algorithm for uplink IoT networks, which improves the efficiency of targeting frequency usage in multi-user systems.

    As the Internet of Things (IoT) network continues to expand, the challenge of managing limited spectrum resources intensifies. Studies have shown that both non-orthogonal multiple access (NOMA) and spectrum sensing have the potential to increase spectrum utilization.
    　　While NOMA and spectrum sensing can ease the spectrum shortage, the combination of them does not reach the upper bound of spectrum utilization due to certain reasons. Also, it faces the challenge of detecting the signal states when multiple users superpose.
    　　To address these problems, a collaborative research team led by Prof. XU Tianhong and HU Honglin from the Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences (CAS), in partnership with VTT Technical Research Centre of Finland, the University of Electro-Communications in Japan, and Shanghai University, proposed an innovative NOMA-based spectrum sensing algorithm for uplink IoT networks, which improves the efficiency of targeting frequency usage in multi-user systems.
    　　The research results were published in the latest issue of IEEE Transactions on Cognitive Communications and Networking.
    　　Focusing on inter-system orthogonal/non-orthogonal aliasing coexistence scenarios, researchers propose an adaptive spectrum sensing technology for the multi-user uplink NOMA system, which harmonizes the advancements in both static and dynamic spectrum efficiency.
    　　Moreover, researchers have derived the closed-form expressions among the number of primary users, user transmission willingness, the power ratio and the false-alarm probability in various sensing processes. These formulas have been validated through numerous simulations.
    　　Furthermore, an adaptive NOMA-based sensing algorithm is designed and showcases an impressive 38.20% improvement in system throughput, compared with state-of-the-art techniques.
    　　This research holds the promise of transforming the landscape of spectrum utilization in the emerging IoT era.
    　　Schematic diagram of inter-system orthogonal/non-orthogonal aliasing coexistence IoT sensing scenarios (Image by SARI)
    　　Contact: XU Tianheng
    　　Shanghai Advanced Research Institute
    　　Email: xuth@sari.ac.cn
    　　

    2024-01-12 more+

    Researchers Design a Novel Hollow-Fiber Cu Penetration Electrode for Efficient CO2 Electroreduction

    A research team from the Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences designed a Cu hollow fiber penetration electrode to electroreduce CO2 in strong acid with effective inhibition of hydrogen evolution reaction (HER). The results were published in Energy & Environmental Science.

    Electrochemical conversion of CO2 into value-added chemical fuels driven by renewable electrical energy has twofold roles in reducing net CO2 emission and in addressing energy consumption.Although considerable progress has been made in CO2 electroreduction, carbonate formation can cause serious CO2 loss. CO2 conversion in acidic electrolyte is an attractive way to overcome CO2 loss, however, the selective reduction remains a challenge.Motivated by this challenge, a research team from the Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences designed a Cu hollow fiber penetration electrode to electroreduce CO2 in strong acid with effective inhibition of hydrogen evolution reaction (HER).The results were published in Energy & Environmental Science on December 13, 2023. By virtue of the unique penetration effect induced by Cu hollow fiber, abundant CO2 molecules were supplied to Cu active sites. Cu surface possessed enough high CO2 coverage, which suppressed HER and facilitated CO2 reduction to C2+ products.Thus, a CO2 single-pass conversion rate exceeding 51% with a C2+ Faradaic efficiency of 73.4% and partial current density of 2.2 A cm-2 was achieved in acidic solution (pH = 0.71). The performance of the Cu penetration electrode approximated to or even outperformed those of the state-of-the-art Cu base catalysts.This work represents an encouraging headway in the design and development of new electrode configurations to realize CO2 electroreduction to high-value C2+ chemicals with scalable applications.
    　　Schematic diagram and electrocatalytic performance comparison of CO2 reduction in acidic media over Cu hollow fiber penetration electrode (image by SARI)
    　　

    2023-12-26 more+

    Researchers Develop COFs Adsorbent for Efficient Gold Recovery

    Most reported COFs have been focused on constructing hydrogen bond interactions inside frameworks to improve the adsorption capacity and gold selectivity, while the effects of intrinsic frameworks on gold capture are unproved.Recently, a research team at the Shanghai Advanced Research Institute (SARI) developed a skeleton engineering of COFs for high-efficiency absorbs towards gold capture.The results were published in Angew. Chem. Int. Ed.


    　　Adsorbents with high capture efficiency and capacity are crucial in precious metal resource recovery. Covalent organic frameworks (COFs), a class of crystalline porous organic materials, are regarded as ideal templates for ions adsorption due to their elaborate designability and modifiability.
    　　However, most reported COFs have been focused on constructing hydrogen bond interactions inside frameworks to improve the adsorption capacity and gold selectivity, while the effects of intrinsic frameworks on gold capture are unproved.
    　　Recently, a research team led by Prof. ZENG Gaofeng and Associate Prof. XU Qing at the Shanghai Advanced Research Institute (SARI), collaborated with Prof. HAN Baohang and Associate Prof. DING Xuesong at Nanoscience National Center for Nanoscience and Technology, developed a skeleton engineering of COFs for high-efficiency absorbs towards gold capture.
    　　The results were published in Angew. Chem. Int. Ed.
    　　Researchers first construct three electron-neutral COFs with diarylamine derivatives. Then, they use the Menshutkin reaction to synthesis ionic COFs containing ionic skeleton which can enhance the column force between Au ions and frameworks.
    　　The adsorption performance is further improved by introducing an ionized skeleton. The ionic COFs exhibit the adsorption capacity of 1834 mg g-1 and reached 90% of the maximum adsorption within 10 mins with good cyclic stability.
    　　The theoretical calculation shows that the transition of binding site from imine bond to ionic nitrogen after the post modification, which helps to enhance coulomb force with gold ions, further improving the adsorption kinetics.This work provides inspirations of designing COFs-based molecular/ion trapping agents.  
    　　Skeleton engineering was adopted to form COFs with diarylamine derivatives and ionized skeletons (Imaged by SARI)
    　　Contact: ZENG Gaofeng
    　　Shanghai Advanced Research Institute
    　　Email:zenggf@sari.ac.cn
    　　

    2023-12-15 more+

    Researchers Propose a Novel Approach for Dimensional Engineering of Covalent Organic Frameworks Derived Carbons

    A research group led by Prof. ZENG Gaofeng and XU Qing at Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences, in collaboration with Prof. HE Yue at Shanghai Jiao Tong University, used template-synthesis strategy to first put forward COFs derived carbons in different dimensions to catalyze CO2RR. The results were published in SusMat on Nov. 10.

    Covalent organic frameworks (COFs) are a special class of materials composed of interconnected organic building blocks held together by strong chemical bonds. Featured with evenly distributed atoms and abundant internal empty space, COFs can be utilized as the starting point for developing functional carbon-based materials.When COFs are subjected to high temperatures, they lose their two-dimensional flat shape and become a three-dimensional structure. In order to obtain the carbon dioxide reduction (CO2RR) catalysts with large porosity, high conductivity and abundance of edge sites for doped heteroatoms, the structure control of COF derived carbon is of vital importance but is still underexplored.Recently, a research group led by Prof. ZENG Gaofeng and XU Qing at Shanghai Advanced Research Institute (SARI) of the Chinese Academy of Sciences, in collaboration with Prof. HE Yue at Shanghai Jiao Tong University, used template-synthesis strategy to first put forward COFs derived carbons in different dimensions to catalyze CO2RR.The results were published in SusMat on Nov. 10.Researchers used different methods to create 1D — 3D carbon materials derived from COFs. For the 1D carbon, a layer of COFs was deposited on carbon nanotubes (CNTs), while for the 2D carbon, COFs were deposited on graphene (Gr). As a comparison, they also directly carbonized the COF precursor to create 3D carbon. The COF precursor used in the experiments was TP-BPY-COF, which was synthesized from specific chemicals using solvothermal methods.Synthesis of 1D — 3D carbon materials derived from COFs (Image by SARI)
    　　EXAFS spectra showed that the resulting COF-derived carbon materials contained plenty of nitrogen (N) sites, which acted as catalytic centers, particularly in the form of CoN5. Among the various catalysts tested, the 1D COF-based catalyst exhibited exceptional performance due to its strong affinity for CO2, a higher number of defective sites, and superior electronic conductivity. These qualities resulted in greater CO2RR activity and selectivity towards the desired product (CO), compared to the 2D and 3D catalysts.The results not only present the significance of tailoring the structure of COF-derived carbons to enhance their effectiveness as catalysts in CO2 reduction reactions, but also provide a new perspective to develop efficient COF-based catalysts. By employing COF-derived carbon materials as catalysts for CO2 electroreduction, CO2 can be potentially converted into valuable chemical compounds or even renewable fuels.
    　　  

    2023-11-30 more+
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