Science China Materials

, Volume 61, Issue 9, pp 1159–1166 | Cite as

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

  • Chunqiu Han (韩春秋)
  • Jue Li (李珏)
  • Zhaoyu Ma (马照宇)
  • Haiquan Xie (谢海泉)
  • Geoffrey I.N. Waterhouse
  • Liqun Ye (叶立群)Email author
  • Tierui Zhang (张铁锐)Email author


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.


black phosphorus quantum dots g-C3N4 photocatalysis CO2 photoreduction 



开发还原二氧化碳生成燃料和有价值化学品的低成本、非金属半导体光催化剂, 是减少二氧化碳浓度的一种有效方案. 本工作通 过简单的静电吸引方法成功地将黑磷量子点(BPQDs)分散在石墨相氮化碳(g-C3N4)载体上, 成功制备了BP@g-C3N4复合材料, 并对其在紫 外-可见光激发下光催化还原CO2的性能进行了研究. 电化学表征, 瞬态吸收光谱和荧光光谱数据表明BPQDs的负载提高了g-C3N4的载流 子分离效率. 在氙灯的照射下, 与g-C3N4(CO的生成速率为2.1 μmol g−1 h−1)相比, BP@g-C3N4复合材料光催化还原CO2活性显著提高(当 BPQDs的负载量为1 wt%时, CO的生成速率为6.54 μmol g−1 h−1). 本工作发展了一种新型的可还原CO2的非金属基光催化剂.



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).

Supplementary material

40843_2018_9245_MOESM0_ESM.pdf (283 kb)
Black phosphorus quantum dot/g-C3N4 composites for enhanced CO2 photoreduction to CO


  1. 1.
    Finlay K, Vogt RJ, Bogard MJ, et al. Decrease in CO2 efflux from northern hardwater lakes with increasing atmospheric warming. Nature, 2015, 519: 215–218CrossRefGoogle Scholar
  2. 2.
    Feldman DR, Collins WD, Gero PJ, et al. Observational determination of surface radiative forcing by CO2 from 2000 to 2010. Nature, 2015, 519: 339–343CrossRefGoogle Scholar
  3. 3.
    Chang X, Wang T, Zhang P, et al. Stable aqueous photoelectrochemical CO2 reduction by a Cu2O dark cathode with improved selectivity for carbonaceous products. Angew Chem Int Ed, 2016, 55: 8840–8845CrossRefGoogle Scholar
  4. 4.
    Zhang L, Zhao ZJ, Gong J. Nanostructured materials for heterogeneous electrocatalytic CO2 reduction and their related reaction mechanisms. Angew Chem Int Ed, 2017, 56: 11326–11353CrossRefGoogle Scholar
  5. 5.
    Li X, Wen J, Low J, et al. Design and fabrication of semiconductor photocatalyst for photocatalytic reduction of CO2 to solar fuel. Sci China Mater, 2014, 57: 70–100CrossRefGoogle Scholar
  6. 6.
    Chang X, Wang T, Gong J. CO2 photo-reduction: insights into CO2 activation and reaction on surfaces of photocatalysts. Energy Environ Sci, 2016, 9: 2177–2196CrossRefGoogle Scholar
  7. 7.
    Dong B, Li M, Chen S, et al. Formation of g-C3N4@Ni(OH)2 honeycomb nanostructure and asymmetric supercapacitor with high energy and power density. ACS Appl Mater Interfaces, 2017, 9: 17890–17896CrossRefGoogle Scholar
  8. 8.
    Yu M, Qu Y, Pan K, et al. Enhanced photoelectric conversion efficiency of dye-sensitized solar cells by the synergetic effect of NaYF4:Er3+/Yb3+ and g-C3N4. Sci China Mater, 2017, 60: 228–238CrossRefGoogle Scholar
  9. 9.
    Liang Q, Li Z, Bai Y, et al. Reduced-sized monolayer carbon nitride nanosheets for highly improved photoresponse for cell imaging and photocatalysis. Sci China Mater, 2017, 60: 109–118CrossRefGoogle Scholar
  10. 10.
    Naseri A, Samadi M, Pourjavadi A, et al. Graphitic carbon nitride (g-C3N4)-based photocatalysts for solar hydrogen generation: recent advances and future development directions. J Mater Chem A, 2017, 5: 23406–23433CrossRefGoogle Scholar
  11. 11.
    Muñoz-Batista MJ, Fontelles-Carceller O, Kubacka A, et al. Effect of exfoliation and surface deposition of MnOx species in g-C3N4: Toluene photo-degradation under UV and visible light. Appl Catal B-Environ, 2017, 203: 663–672CrossRefGoogle Scholar
  12. 12.
    Kang S, Zhang L, Yin C, et al. Fast flash frozen synthesis of holey few-layer g-C3N4 with high enhancement of photocatalytic reactive oxygen species evolution under visible light irradiation. Appl Catal B-Environ, 2017, 211: 266–274CrossRefGoogle Scholar
  13. 13.
    Cao S, Huang Q, Zhu B, et al. Trace-level phosphorus and sodium co-doping of g-C3N4 for enhanced photocatalytic H2 production. J Power Sources, 2017, 351: 151–159CrossRefGoogle Scholar
  14. 14.
    Guo S, Tang Y, Xie Y, et al. P-doped tubular g-C3N4 with surface carbon defects: Universal synthesis and enhanced visible-light photocatalytic hydrogen production. Appl Catal B-Environ, 2017, 218: 664–671CrossRefGoogle Scholar
  15. 15.
    Li K, Huang Z, Zeng X, et al. Synergetic effect of Ti3+ and oxygen doping on enhancing photoelectrochemical and photocatalytic properties of TiO2/g-C3N4 heterojunctions. ACS Appl Mater Interfaces, 2017, 9: 11577–11586CrossRefGoogle Scholar
  16. 16.
    Wang K, Li Q, Liu B, et al. Sulfur-doped g-C3N4 with enhanced photocatalytic CO2-reduction performance. Appl Catal B-Environ, 2015, 176–177: 44–52CrossRefGoogle Scholar
  17. 17.
    Ran J, Ma TY, Gao G, et al. Porous P-doped graphitic carbon nitride nanosheets for synergistically enhanced visible-light photocatalytic H2 production. Energy Environ Sci, 2015, 8: 3708–3717CrossRefGoogle Scholar
  18. 18.
    Luo J, Zhou X, Ma L, et al. Enhancing visible-light photocatalytic activity of g-C3N4 by doping phosphorus and coupling with CeO2 for the degradation of methyl orange under visible light irradiation. RSC Adv, 2015, 5: 68728–68735CrossRefGoogle Scholar
  19. 19.
    Zhu Z, Lu Z, Wang D, et al. Construction of high-dispersed Ag/Fe3O4/g-C3N4 photocatalyst by selective photo-deposition and improved photocatalytic activity. Appl Catal B-Environ, 2016, 182: 115–122CrossRefGoogle Scholar
  20. 20.
    Kong L, Dong Y, Jiang P, et al. Light-assisted rapid preparation of a Ni/g-C3N4 magnetic composite for robust photocatalytic H2 evolution from water. J Mater Chem A, 2016, 4: 9998–10007CrossRefGoogle Scholar
  21. 21.
    Lan M, Fan G, Yang L, et al. Enhanced visible-light-induced photocatalytic performance of a novel ternary semiconductor coupling system based on hybrid Zn–In mixed metal oxide/g-C3N4 composites. RSC Adv, 2015, 5: 5725–5734CrossRefGoogle Scholar
  22. 22.
    Han J, Zou HY, Liu ZX, et al. Efficient visible-light photocatalytic heterojunctions formed by coupling plasmonic Cu2−xSe and gra-phitic carbon nitride. New J Chem, 2015, 39: 6186–6192CrossRefGoogle Scholar
  23. 23.
    Rong X, Qiu F, Yan J, et al. Coupling with a narrow-band-gap semiconductor for enhancement of visible-light photocatalytic activity: preparation of Bi2S3/g-C3N4 and application for degradation of RhB. RSC Adv, 2015, 5: 24944–24952CrossRefGoogle Scholar
  24. 24.
    Ong WJ, Tan LL, Chai SP, et al. Surface charge modification via protonation of graphitic carbon nitride (g-C3N4) for electrostatic self-assembly construction of 2D/2D reduced graphene oxide (rGO)/g-C3N4 nanostructures toward enhanced photocatalytic reduction of carbon dioxide to methane. Nano Energy, 2015, 13: 757–770CrossRefGoogle Scholar
  25. 25.
    Feng Y, Shen J, Cai Q, et al. The preparation and properties of a g- C3N4/AgBr nanocomposite photocatalyst based on protonation pretreatment. New J Chem, 2015, 39: 1132–1138CrossRefGoogle Scholar
  26. 26.
    Ma L, Fan H, Fu K, et al. Protonation of graphitic carbon nitride (g-C3N4) for an electrostatically self-assembling carbon@g-C3N4 core–shell nanostructure toward high hydrogen evolution. ACS Sustain Chem Eng, 2017, 5: 7093–7103CrossRefGoogle Scholar
  27. 27.
    Shi L, Chang K, Zhang H, et al. Drastic enhancement of photocatalytic activities over phosphoric acid protonated porous g-C3N4 nanosheets under visible light. Small, 2016, 12: 4431–4439CrossRefGoogle Scholar
  28. 28.
    Dhanabalan SC, Ponraj JS, Guo Z, et al. Emerging trends in phosphorene fabrication towards next generation devices. Adv Sci, 2017, 4: 1600305CrossRefGoogle Scholar
  29. 29.
    Li L, Yu Y, Ye GJ, et al. Black phosphorus field-effect transistors. Nat Nanotechnol, 2014, 9: 372–377CrossRefGoogle Scholar
  30. 30.
    Zhu M, Kim S, Mao L, et al. Metal-free photocatalyst for H2 evolution in visible to near-infrared region: black phosphorus/graphitic carbon nitride. J Am Chem Soc, 2017, 139: 13234–13242CrossRefGoogle Scholar
  31. 31.
    Zhu M, Cai X, Fujitsuka M, et al. Au/La2Ti2O7 nanostructures sensitized with black phosphorus for plasmon-enhanced photocatalytic hydrogen production in visible and near-infrared light. Angew Chem Int Ed, 2017, 56: 2064–2068CrossRefGoogle Scholar
  32. 32.
    Uk Lee H, Lee SC, Won J, et al. Stable semiconductor black phosphorus (BP)@titanium dioxide (TiO2) hybrid photocatalysts. Sci Rep, 2015, 5: 8691CrossRefGoogle Scholar
  33. 33.
    Xu JY, Gao LF, Hu CX, et al. Preparation of large size, few-layer black phosphorus nanosheets via phytic acid-assisted liquid exfoliation. Chem Commun, 2016, 52: 8107–8110CrossRefGoogle Scholar
  34. 34.
    Wang L, Xu Q, Xu J, et al. Synthesis of hybrid nanocomposites of ZIF-8 with two-dimensional black phosphorus for photocatalysis. RSC Adv, 2016, 6: 69033–69039CrossRefGoogle Scholar
  35. 35.
    Wang H, Yang X, Shao W, et al. Ultrathin black phosphorus nanosheets for efficient singlet oxygen generation. J Am Chem Soc, 2015, 137: 11376–11382CrossRefGoogle Scholar
  36. 36.
    Yang D, Yang G, Yang P, et al. Assembly of au plasmonic photothermal agent and iron oxide nanoparticles on ultrathin black phosphorus for targeted photothermal and photodynamic cancer therapy. Adv Funct Mater, 2017, 27: 1700371CrossRefGoogle Scholar
  37. 37.
    Hanlon D, Backes C, Doherty E, et al. Liquid exfoliation of solventstabilized few-layer black phosphorus for applications beyond electronics. Nat Commun, 2015, 6: 8563CrossRefGoogle Scholar
  38. 38.
    Yu J, Wang K, Xiao W, et al. Photocatalytic reduction of CO2 into hydrocarbon solar fuels over g-C3N4–Pt nanocomposite photocatalysts. Phys Chem Chem Phys, 2014, 16: 11492–11501CrossRefGoogle Scholar
  39. 39.
    Ong WJ, Tan LL, Chai SP, et al. Heterojunction engineering of graphitic carbon nitride (g-C3N4) via Pt loading with improved daylight-induced photocatalytic reduction of carbon dioxide to methane. Dalton Trans, 2015, 44: 1249–1257CrossRefGoogle Scholar
  40. 40.
    Wang H, Sun Z, Li Q, et al. Surprisingly advanced CO2 photocatalytic conversion over thiourea derived g-C3N4 with water vapor while introducing 200–420 nm UV light. J CO2 Utilization, 2016, 14: 143–151CrossRefGoogle Scholar
  41. 41.
    Li H, Gao Y, Wu X, et al. Fabrication of heterostructured g-C3N4/Ag-TiO2 hybrid photocatalyst with enhanced performance in photocatalytic conversion of CO2 under simulated sunlight irradiation. Appl Surf Sci, 2017, 402: 198–207CrossRefGoogle Scholar
  42. 42.
    Lin L, Hou C, Zhang X, et al. Highly efficient visible-light driven photocatalytic reduction of CO2 over g-C3N4 nanosheets/tetra(4- carboxyphenyl)porphyrin iron(III) chloride heterogeneous catalysts. Appl Catal B-Environ, 2018, 221: 312–319CrossRefGoogle Scholar
  43. 43.
    Wang JC, Yao HC, Fan ZY, et al. Indirect Z-scheme BiOI/g-C3N4 photocatalysts with enhanced photoreduction CO2 activity under visible light irradiation. ACS Appl Mater Interfaces, 2016, 8: 3765–3775CrossRefGoogle Scholar
  44. 44.
    Wang M, Shen M, Zhang L, et al. 2D-2D MnO2/g-C3N4 heterojunction photocatalyst: In-situ synthesis and enhanced CO2 reduction activity. Carbon, 2017, 120: 23–31CrossRefGoogle Scholar
  45. 45.
    Li M, Zhang L, Wu M, et al. Mesostructured CeO2/g-C3N4 nanocomposites: Remarkably enhanced photocatalytic activity for CO2 reduction by mutual component activations. Nano Energy, 2016, 19: 145–155CrossRefGoogle Scholar
  46. 46.
    Xu J, Li Y, Peng S, et al. Eosin Y-sensitized graphitic carbon nitride fabricated by heating urea for visible light photocatalytic hydrogen evolution: the effect of the pyrolysis temperature of urea. Phys Chem Chem Phys, 2013, 15: 7657–7665CrossRefGoogle Scholar
  47. 47.
    Ma Z, Li P, Ye L, et al. Oxygen vacancies induced exciton dissociation of flexible BiOCl nanosheets for effective photocatalytic CO2 conversion. J Mater Chem A, 2017, 5: 24995–25004CrossRefGoogle Scholar
  48. 48.
    Bai Y, Shi X, Wang PQ, et al. Photocatalytic mechanism regulation of bismuth oxyhalogen via changing atomic assembly method. ACS Appl Mater Interfaces, 2017, 9: 30273–30277CrossRefGoogle Scholar
  49. 49.
    Wang H, Jiang S, Chen S, et al. Insights into the excitonic processes in polymeric photocatalysts. Chem Sci, 2017, 8: 4087–4092CrossRefGoogle Scholar
  50. 50.
    Wang H, Chen S, Yong D, et al. Giant electron–hole interactions in confined layered structures for molecular oxygen activation. J Am Chem Soc, 2017, 139: 4737–4742CrossRefGoogle Scholar
  51. 51.
    Wang H, Sun X, Li D, et al. Boosting hot-electron generation: exciton dissociation at the order–disorder interfaces in polymeric photocatalysts. J Am Chem Soc, 2017, 139: 2468–2473CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Chunqiu Han (韩春秋)
    • 1
  • Jue Li (李珏)
    • 1
  • Zhaoyu Ma (马照宇)
    • 1
  • Haiquan Xie (谢海泉)
    • 1
  • Geoffrey I.N. Waterhouse
    • 4
  • Liqun Ye (叶立群)
    • 1
    • 3
    Email author
  • Tierui Zhang (张铁锐)
    • 2
    • 5
    Email author
  1. 1.Engineering Technology Research Center of Henan Province for Solar Catalysis, College of Chemistry and Pharmaceutical EngineeringNanyang Normal UniversityNanyangChina
  2. 2.Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and ChemistryChinese Academy of SciencesBeijingChina
  3. 3.Key Laboratory for Photonic and Electric Bandgap Materials, Ministry of EducationHarbin Normal UniversityHarbinChina
  4. 4.School of Chemical SciencesThe University of AucklandAucklandNew Zealand
  5. 5.University of Chinese Academy of SciencesBeijingChina

Personalised recommendations