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SCIENCE CHINA Materials, Volume 63 , Issue 7 : 1113-1141(2020) https://doi.org/10.1007/s40843-020-1304-3

Reticular chemistry in electrochemical carbon dioxide reduction

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  • ReceivedJan 10, 2020
  • AcceptedMar 17, 2020
  • PublishedApr 28, 2020

Abstract


Funded by

This work was financially supported by the National Natural Science Foundation of China(21671096,11775105)

and the Shenzhen Peacock Plan(KQTD2016022620054656)


Acknowledgment

This work was financially supported by the National Natural Science Foundation of China (21671096 and 11775105), and Shenzhen Peacock Plan (KQTD2016022620054656).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Wang Y and Li Y conceived and wrote the paper under the supervision of Lu Z. Wang Z, Allan P and Zhang F helped in the revision of this review. All authors contributed to the general discussion.


Author information

Yanfang Wang received his BE degree from Central South University in 2014 and MS degree from Fudan University in 2017. Now, he is a PhD student at Southern University of Science and Technology (SUSTech), China, jointly with the University of Birmingham, UK. His research interests mainly focus on supercapacitors and lithium-ion batteries.


Zhouguang Lu is currently a professor in the Department of Materials Science and Engineering, SUSTech, China. He received his PhD degree from the City University of Hong Kong in 2009. He is the recipient of Fulbright Fellowship of USA Government in 2008–2009 and the Overseas High-Caliber Personnel (Level B) of Shenzhen Government in 2013. His research mainly covers the design and synthesis of nanostructures and their applications in energy storage and conversion with focus on lithium/sodium-ion and -air batteries. He has authored more than 160 peer-review journal papers with total citations more than 5600 and H-index of 46.


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  • Figure 1

    A typical system for ECR. ECR and OER occur on the cathode and anode, producing C products and oxygen, respectively. Proton-exchange membranes allow proton transfer across the electrolyte and prevent unwanted ion migrations.

  • Figure 2

    Possible pathways from gaseous CO2 to valuable C products. Every step refers to a PCET, in which the proton and electron simultaneously transfer to the adsorbed species.

  • Figure 3

    (a) Design and synthesis of COF-366-Co and COF-367-Co. Reprinted with permission from Ref. [121]. Copyright 2015, The American Association for the Advancement of Science (AAAS). (b) Systematic modulation of COF-366-Co through remote functionalization. Reprinted with permission from Ref. [125]. Copyright 2018, American Chemical Society. (c) Illustration of the pores in COF-366. Reprinted with permission from Ref. [120]. Copyright 2011, American Chemical Society. (d) Cyclic voltammograms (in DMF with tetrabutylammonium hexafluorophosphate as the electrolyte) and (e) current densities (at −0.67 V vs. RHE in 0.5 mol L−1 aqueous potassium bicarbonate buffer) of modulated COFs [125].

  • Figure 4

    (a) Illustration of a portion of the crystal structure of MOF-525 in porphyrin free-base form, including the chemical structure of the TCPP linker and the Zr6-based node. Reprinted with permission from Ref. [128]. Copyright 2012, American Chemical Society. (b) Illustration of the surface structure of Fe-MOF-525 electrode, showing the mechanism of redox hopping between neighboring Fe-TCPP sites. Reprinted with permission from Ref. [129]. Copyright 2015, American Chemical Society. (c) Illustration of the principal for MOF EPD film growth. Reprinted with permission from Ref. [132]. Copyright 2014, Wiley-VCH. (d) FE of ECR on Fe-MOF-525 electrode [129].

  • Figure 5

    (a) Co-metalated TCPP units. (b) Illustration of the 3D MOF assembly. Co, orange spheres; O, red spheres; C, black spheres; N, blue spheres; Al, light-blue octahedra; and pyrrole ring, blue. (c) Functional principles of ECR in the integrated system. Reprinted with permission from Ref. [131]. Copyright 2015, American Chemical Society.

  • Figure 6

    (a) Schematic representation of the fabrication process of Re-MOF on the functionalized FTO substrate in a layer-by-layer fashion. (b) Illustration of the preferred charge transfer pathway in epitaxial Re-MOF along the [001] direction. Reprinted with permission from Ref. [135]. Copyright 2016, The Royal Society of Chemistry. (c) Proposed structures of the cobalt phthalocyanine-based COF series. Reprinted with permission from Ref. [137]. Copyright 2018, Wiley-VCH.

  • Figure 7

    (a) Schematic fabrication of the Zn-based MOF electrode. Scanning electron microscopy (SEM) images of (b) the cross section of the electrode, (c) electrode surface and (d) the amplified electrode surface. (e) The possible pathway for electrochemical reduction of CO2 to CH4 on the Zn-MOF/CP cathode in ILs. (f) Cyclic voltammetry (CV) curves and (g) current density profiles (at −2.2 V vs. Ag/Ag+) in different ILs: 1-BmimBF4; 2-BmimOTf; 3-BmimPF6; 4-BmimClO4. Reprinted with permission from Ref. [151]. Copyright 2015, The Royal Society of Chemistry.

  • Figure 8

    (a) Schematic representation of solvothermal-deposition in MOFs (SIM) to install single-site Cu(II) into the NU-1000 thin film and the electrochemical reduction of Cu(II) to generate metallic Cu nanoparticles. Top-view SEM images of the (b) NU-1000 thin film and (c) Cu-SIM NU-1000 thin film. (d) Cross-section SEM image of the Cu-SIM NU-1000 thin film (left part) and energy dispersive X-ray spectroscopy (EDS) line scan results (right part). (e) Cross-section SEM image of the reduced Cu-SIM NU-1000 thin film (left part) and EDS line scan results (right part). Reprinted with permission from Ref. [164]. Copyright 2017, American Chemical Society.

  • Figure 9

    (a) Schematic representation of the functionalized MOF (UiO-66) for CO2 separation. Reprinted with permission from Ref. [176]. Copyright 2017, Springer Nature Publishing Group. (b) Flexible design on MOF pores by varying the length of linkers for gas separation. Reprinted with permission from Ref. [171]. Copyright 2018, Springer Nature Publishing Group. (c) Structural schematic diagram of GDE with Cu-based MOF as CO2 capturer. Reprinted with permission from Ref. [178]. Copyright 2017, American Chemical Society.

  • Figure 10

    (a) Scheme for COF-300 reduction. In the space-filling diagrams, carbon and nitrogen atoms are represented as gray and blue spheres, respectively. Only the hydrogen atoms on the imine and amine linkage are shown (in pink) for clarity. (b) Illustration of the molecularly defined interface created by COF-300-AR on a flat silver electrode. (c) Scheme of the mechanism of concerted CO2 reduction taking place at the interface. (d)13C cross polarization magic angle spinning nuclear magnetic resonance (CP-MAS NMR) results showing the formation of carbamate intermediate during CO2 reduction process. FEs for (e) CO and (f) H2 production on the concerted electrode. Reprinted with permission from Ref. [180]. Copyright 2018, Cell Press.

  • Figure 11

    (a) Schematic illustration of the route to synthesize ZIF-8 and N-doped carbon (NC). (b) Transmission electron microscopy (TEM) images of ZIF-8 (upper) and NC-900 (bottom). The agglomeration of dispersed carbon nanoparticles in NC-900 is clear. (c) FEs for CO (upper) and H2 (bottom). The number following NC refers to the pyrolytic temperature. Reprinted with permission from Ref. [189]. Copyright 2018, American Chemical Society. (d) Schematic presentation of enhanced interparticle conductivity and mass transport in MWCNT supported NC. (e) TEM images of ZIF-CNT (upper) and the derived ZIF-CNT-FA-p (bottom). (f) FEs for CO (upper) and H2 (bottom). FA is short for furfuryl alcohol, acting as an additional carbon source. The p refers to pyrolyzed sample. Reprinted with permission from Ref. [196]. Copyright 2018, The Royal Society of Chemistry.

  • Figure 12

    (a) Schematic synthesis process of oxide-derived Cu/carbon catalysts. SEM images of (b) HKUST-1 and (c) OD Cu/C-1000. The number refers to the pyrolytic temperature. (d) TEM image of OD Cu/C-1000. (e) Magnified TEM image and selected area electron diffraction (SAED) patterns of OD Cu/C-1000. (f) Production rates and (g) FEs for ECR products on OD Cu/C-1000 electrode. Reprinted with permission from Ref. [201]. Copyright 2017, American Chemical Society.

  • Figure 13

    (a) Scheme of the formation of Ni SAs/N-C. (b) TEM and (c) high-angle annular dark-field scanning TEM (HAADF-STEM) images of Ni SAs/N-C. (d) Corresponding SAED pattern of an individual rhombic dodecahedron. (e, f) Magnified HAADF-STEM images of Ni SAs/N-C. The Ni single atoms are marked with red circles. (g) Corresponding EDS mapping images revealing the homogeneous distribution of Ni and N on the carbon support. (h) X-ray absorption near-edge structure (XANES) spectra and corresponding fitting curves of Ni SAs/N-C. Inset is the proposed Ni−N3 moiety. (i) FEs for CO on Ni SAs/N-C and Ni NPs/N-C. NP refers to nanoparticle, formed by the accumulation of single atoms and crystal growth when excess Ni ions were adsorbed. (j) Proposed reaction paths for CO2 electroreduction on Ni SAs/N-C. Reprinted with permission from Ref. [211]. Copyright 2017, American Chemical Society.

  • Figure 14

    (a) Schematic representation of the various Fe-N-C materials obtained upon pyrolysis: the amount of Fe nanoparticles increases with increased Fe loading. Fe atoms are represented in red, C atoms in grey and N atoms in blue. The graphitic shell typically surrounding Fe nanoparticles after pyrolysis is not represented for clarity. (b, c) 57Fe Mössbauer absorption spectra of Fe-N-C materials, as labelled on the figures. FEs for (d) CO and (e) H2 formation of those materials. Reprinted with permission form Ref. [214]. Copyright 2017, American Chemical Society.

  • Figure 15

    (a) Schematic formation of Co single sites in the Zn/Co bimetallic ZIF. Reprinted with permission from Ref. [207]. Copyright 2016, Wiley-VCH. (b) SEM and (c, d) STEM images of Co-HNC. (e–i) Corresponding electron energy loss (EEL) mapping images indicating homogeneous distribution of N, O, and Co throughout the hollow carbon structure. (j) EEL spectra of Co-HNC. (k, l) HAADF-STEM images of Co-HNC at different areas. Part of Co single atoms are marked with red circles. (m) Atomic contents of N species in Co-HNC and Co NP-SNC (solid nitrogen-doped carbon embedded with Co nanoparticle). Inset is the proposed Co−C2N2 moiety. (n) Productivity (left Y-axis) and FE (right Y-axis) of Co-HNC. Reprinted with permission from Ref. [219]. Copyright 2018, Wiley-VCH.