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SCIENCE CHINA Materials, Volume 61, Issue 9: 1159-1166(2018) https://doi.org/10.1007/s40843-018-9245-y

Black phosphorus quantum dot/g-C3N4 composites for enhanced CO2 photoreduction to CO

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  • ReceivedFeb 1, 2018
  • AcceptedMar 6, 2018
  • PublishedMar 21, 2018

Abstract

The development of low cost, metal free semiconductor photocatalysts for CO2 reduction to fuels and valuable chemical feedstocks is a practically imperative for reducing anthropogenic CO2 emissions. In this work, black phosphorus quantum dots (BPQDs) were successfully dispersed on a graphitic carbon nitride (g-C3N4) support via a simple electrostatic attraction approach, and the activities of BP@g-C3N4 composites were evaluated for photocatalytic CO2 reduction. The BP@g-C3N4 composites displayed improved carrier separation efficiency and higher activities for photocatalytic CO2 reduction to CO (6.54 µmol g−1 h−1 at the optimum BPQDs loading of 1 wt%) compared with pure g-C3N4(2.65 µmol g−1 h−1). This work thus identifies a novel approach towards metal free photocatalysts for CO2 photoreduction.


Funded by

the National Natural Science Foundation of China(51502146,U1404506,21671113,51772305,51572270,U1662118)

the International Partnership Program of Chinese Academy of Science(GJHZ1819)

the Royal Society-Newton Advanced Fellowship(NA170422)

supported by Open Fund(PEBM201702)

Ministry of Education(Harbin,Normal,University)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (51502146, U1404506, 21671113, 51772305, 51572270, and U1662118), the International Partnership Program of Chinese Academy of Sciences (GJHZ1819), the Royal Society-Newton Advanced Fellowship (NA170422) and supported by Open Fund (PEBM201702) of Key Laboratory for Photonic and Electric Bandgap Materials, Ministry of Education (Harbin Normal University).


Interest statement

The authors declare no conflict of interest.


Contributions statement

Han C and Ye L conceived the idea of the project. Han C conducted the synthesis of materials and performed the characterizations and photocatalytic tests. Ye L and Zhang T analyzed the data. Han C drafted the manuscript. Waterhouse G and Zhang T revised the manuscript. All authors participated in the general discussion of the manuscript.


Author information

Chunqiu Han obtained her BS degree from Nanyang Normal University in 2016. She then moved to the College of Chemistry and Pharmaceutical Engineering in Nanyang Normal University for her Master degree. She is interested in developing new photocatalyst for CO2 reduction.


Liqun Ye obtained his BSc degree from Qiqihar University in 2008, and his PhD degree from Wuhan University in 2013. At present, he works in Nanyang Normal University. His current research concentrates on the synthesis of 2D photo-functional materials and their applications in the fields of environment remediation and solar fuel production.


Tierui Zhang is a full Professor in the Technical Institute of Physics and Chemistry, CAS. He received his BSc in chemistry in 1998, and PhD in organic chemistry in 2003 from Jilin University in China. After that, he did postdoctoral study in Max Planck Institute of Colloids and Interfaces, University of Alberta, University of Arkansas and University of California-Riverside, respectively. His research activity focuses on catalyst nanomaterials for clean and efficient production and utilization of hydrogen.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


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  • Figure 1

    (a) XRD patterns of g-C3N4 and BP@g-C3N4; (b) solid-state 31P NMR spectra of g-C3N4 and BP@g-C3N4; (c) HRTEM image and (d) EDS element mapping of BP@g-C3N4. The BPQDs loading was 1 wt%.

  • Figure 2

    XPS spectra of g-C3N4 and BP@g-C3N4: (a) P 2p; (b) O 1s; (c) N 1s and (d) C 1s. The BPQDs loading was 1 wt%.

  • Figure 3

    Rates of CO generation over BP@g-C3N4 photocatalysts under Xenon lamp irradiation for 4 h.

  • Figure 4

    (a) Photocurrent response, (b) electrochemical impedance, (c) time-resolved PL, (d) transient absorption of g-C3N4 and BP@g-C3N4.

  • Figure 5

    Time-dependent absorption spectra of TMB oxidation for g-C3N4 (a) and BP@g-C3N4 (b), time-dependent absorption spectra of NBT oxidation for g-C3N4 (c) and BP@g-C3N4 (d), ESR spectra of 1O2 (e) and O2•− (f) generated from g-C3N4 and BP@g-C3N4.

  • Table 1   Performance comparison of g-CN based photocatalysts for CO conversion

    Photocatalysts

    300 WXe lamp

    CO

    CH4

    Ref.

    µmol g−1 h−1

    g-C3N4

    full

    2.10

    0.24

    40

    Ag-TiO2/g-C3N4

    full

    6.33

    9.33

    41

    FeTCPP/g-C3N4

    λ > 420 nm

    1.14

    0.05

    42

    BiOI/g-C3N4

    full

    3.44

    0.16

    43

    MnO2/g-C3N4

    full

    3.4

    /

    44

    CeO2/g-C3N4

    full

    10.16

    13.9

    45

    g-C3N4

    full

    2.65

    0.67

    This work

    BP@g-C3N4

    full

    6.54

    0.29

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