Environmental Science and Pollution Research

, Volume 23, Issue 18, pp 18369–18378 | Cite as

Ag/Ag2SO3 plasmonic catalysts with high activity and stability for CO2 reduction with water vapor under visible light

  • Da Wang
  • Yan Yu
  • Zhipeng Zhang
  • Huiying Fang
  • Jianmeng Chen
  • Zhiqiao He
  • Shuang SongEmail author
Research Article


The conversion of CO2 into useful raw materials for fuels and chemicals by solar energy is described using a plasmonic photocatalyst comprised of Ag supported on Ag2SO3 (Ag/Ag2SO3) fabricated by a facile solid-state ion-exchange method and subsequent reduction with hydrazine hydrate. The optimum molar ratio of Ag0/Ag+ was 5 %. Visible light irradiation (>400 nm) of the Ag/Ag2SO3 powder in the presence of CO2 and water vapor led to the formation of CH4 and CO with a quantum yield of 0.126 %, and an energy returned on energy invested of 0.156 %. The Ag/Ag2SO3 retained high catalytic activity after ten successive experimental cycles. The catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy with energy-dispersive X-ray analysis, UV/Vis absorption spectroscopy, and Brunauer-Emmett-Teller analyses, as well as photocurrent action spectroscopy. It is proposed that the photocatalytic activity of the catalysts is initiated by energy conversion from incident photons to localized surface plasmon resonance oscillations of silver nanoparticles. This plasmonic energy is transferred to the Ag2SO3 by direct electron transfer and/or resonant energy transfer, causing the separation of photogenerated electron/hole pairs.


Ag/Ag2SO3 Plasmonic photocatalysts CO2 reduction 



This work was supported by the Program for Changjiang Scholars and Innovative Research Team in University (Grant IRT13096), the National Natural Science Foundation of China (Grants 21076196, 21177115, and 21477117), and the Zhejiang Provincial Natural Science Foundation of China (Grants LR13B070002 and LR14E080001).


  1. Abou Asi M, Zhu LF, He C, Sharma VK, Shu D, Li SZ, Yang JN, Xiong Y (2013) Visible-light-harvesting reduction of CO2 to chemical fuels with plasmonic Ag@AgBr/CNT nanocomposites. Catal Today 216:268–275CrossRefGoogle Scholar
  2. Alvaro M, Cojocaru B, Ismail AA, Petrea N, Ferrer B, Harraz FA, Parvulescu VI, Garcia H (2010) Visible-light photocatalytic activity of gold nanoparticles supported on template-synthesized mesoporous titania for the decontamination of the chemical warfare agent Soman. Appl Catal B Environ 99:191–197CrossRefGoogle Scholar
  3. An CH, Wang JZ, Jiang W, Zhang MY, Ming XJ, Wang ST, Zhang QH (2012) Strongly visible-light responsive plasmonic shaped AgX:Ag (X = Cl, Br) nanoparticles for reduction of CO2 to methanol. Nanoscale 4:5646–5650CrossRefGoogle Scholar
  4. Aresta M, Dibenedetto A, Angelini A (2014) Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels: technological use of CO2. Chem Rev 114:1709–1742CrossRefGoogle Scholar
  5. Chun WJ, Ishikawa A, Fujisawa H, Takata T, Kondo JN, Hara M, Kawai M, Matsumoto Y, Domen K (2003) Conduction and valence band positions of Ta2O5, TaON, and Ta3N5 by UPS and electrochemical methods. J Phys Chem B 107:1798–1803CrossRefGoogle Scholar
  6. Cushing SK, Wu NQ (2013) Plasmon-enhanced solar energy harvesting. Electrochem Soc Inter 22:63–67Google Scholar
  7. Cushing SK, Li JT, Meng FK, Senty TR, Suri S, Zhi MJ, Li M, Bristow AD, Wu NQ (2012) Photocatalytic activity enhanced by plasmonic resonant energy transfer from metal to semiconductor. J Am Chem Soc 134:15033–15041CrossRefGoogle Scholar
  8. Dhakshinamoorthy A, Navalon S, Corma A, Garcia H (2012) Photocatalytic CO2 reduction by TiO2 and related titanium containing solids. Energy Environ Sci 5:9217–9233CrossRefGoogle Scholar
  9. Dong C, Wu KL, Wei XW, Wang J, Liu L, Hu Y, Xia SH (2014) Preparation of Ag2SO3 sub-microparticles with high visible-light photocatalytic activity. Micro Nano Lett 9:417–420CrossRefGoogle Scholar
  10. Fan XX, Yu T, Wang Y, Zheng J, Gao L, Li ZS, Ye JH, Zou ZG (2008) Role of phosphorus in synthesis of phosphated mesoporous TiO2 photocatalytic materials by EISA method. Appl Surf Sci 254:5191–5198CrossRefGoogle Scholar
  11. Guan GQ, Kida T, Harada T, Isayama M, Yoshida A (2003) Photoreduction of carbon dioxide with water over K2Ti6O13 photocatalyst combined with Cu/ZnO catalyst under concentrated sunlight. Appl Catal A 249:11–18CrossRefGoogle Scholar
  12. Guijarro N, Prévot MS, Sivula K (2015) Surface modification of semiconductor photoelectrodes. Phys Chem Chem Phys 17:15655–15674CrossRefGoogle Scholar
  13. Habisreutinger SN, Schmidt-Mende L, Stolarczyk JK (2013) Photocatalytic reduction of CO2 on TiO2 and other semiconductors. Angew Chem Int Ed 52:7372–7408CrossRefGoogle Scholar
  14. Happel M, Lykhach Y, Tsud N, Skala T, Prince KC, Matolin V, Libuda J (2011) Mechanism of sulfur poisoning and storage: adsorption and reaction of SO2 with stoichiometric and reduced ceria films on Cu(111). J Phys Chem C 115:19872–19882CrossRefGoogle Scholar
  15. He ZQ, Tang JT, Shen J, Chen JM, Song S (2016) Enhancement of photocatalytic reduction of CO2 to CH4 over TiO2 nanosheets by modifying with sulfuric acid. Appl Surf Sci 364:416–427CrossRefGoogle Scholar
  16. Hou WB, Cronin SB (2013) A review of surface plasmon resonance-enhanced photocatalysis. Adv Funct Mater 23:1612–1619CrossRefGoogle Scholar
  17. Li TB, Chen G, Zhou C, Shen ZY, Jin RC, Sun JX (2011) New photocatalyst BiOCl/BiOI composites with highly enhanced visible light photocatalytic performances. Dalton Trans 40:6751–6758CrossRefGoogle Scholar
  18. Li Q, Zhang CH, Ma JM, Wang GZ, Ng DHL (2014) Improved photocatalytic performance of the ultra-small Ag nanocrystallite-decorated TiO2 hollow sphere heterostructures. ChemCatChem 6:1392–1400Google Scholar
  19. Liu LJ, Zhao CY, Zhao HL, Pitts D, Li Y (2013) Porous microspheres of MgO-patched TiO2 for CO2 photoreduction with H2O vapor: temperature-dependent activity and stability. Chem Commun 49:3664–3666CrossRefGoogle Scholar
  20. Long JL, Chang HJ, Gu Q, Xu J, Fan LZ, Wang SC, Zhou YG, Wei W, Huang L, Wang XX, Liu P (2014) Gold-plasmon enhanced solar-to-hydrogen conversion on the {001} facets of anatase TiO2 nanosheets. Energy Environ Sci 7:973–977CrossRefGoogle Scholar
  21. Lou ZZ, Wang ZY, Huang BB, Dai Y (2014) Synthesis and activity of plasmonic photocatalysts. ChemCatChem 6:2456–2476CrossRefGoogle Scholar
  22. Mao J, Li K, Peng TY (2013) Recent advances in the photocatalytic CO2 reduction over semiconductors. Catal Sci Technol 3:2481–2498CrossRefGoogle Scholar
  23. McEvoy JG, Cui WQ, Zhang ZS (2014) Synthesis and characterization of Ag/AgCl-activated carbon composites for enhanced visible light photocatalysis. Appl Catal B Environ 144:702–712CrossRefGoogle Scholar
  24. Nehl CL, Hafner JH (2008) Shape-dependent plasmon resonances of gold nanoparticles. J Mater Chem 18:2415–2419CrossRefGoogle Scholar
  25. Nethercot AH (1974) Prediction of Fermi energies and photoelectric thresholds based on electronegativity concepts. Phys Rev Lett 33:1088–1091CrossRefGoogle Scholar
  26. Ren N, Li R, Chen LM, Wang GC, Liu D, Wang YJ, Zheng L, Tang W, Yu XQ, Jiang HD, Liu H, Wu NQ (2012) In situ construction of a titanate-silver nanoparticle-titanate sandwich nanostructure on a metallic titanium surface for bacteriostatic and biocompatible implants. J Mater Chem 22:19151–19160CrossRefGoogle Scholar
  27. Song CS (2006) Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing. Catal Today 115:2–32CrossRefGoogle Scholar
  28. Song S, Hong FY, He ZQ, Wang HY, Xu XH, Chen JM (2011) Influence of zirconium doping on the activities of zirconium and iodine co-doped titanium dioxide in the decolorization of methyl orange under visible light irradiation. Appl Surf Sci 257:10101–10108CrossRefGoogle Scholar
  29. Song GX, Xin F, Chen JS, Yin XH (2014) Photocatalytic reduction of CO2 in cyclohexanol on CdS-TiO2 heterostructured photocatalyst. Appl Catal A Gen 473:90–95CrossRefGoogle Scholar
  30. Tauc J (1968) Optical properties and electronic structure of amorphous Ge and Si. Mater Res Bull 3:37–46CrossRefGoogle Scholar
  31. Tian ZB, Wang LQ, Jia LS, Li QB, Song QQ, Su S, Yang H (2013) A novel biomass coated Ag-TiO2 composite as a photoanode for enhanced photocurrent in dye-sensitized solar cells. RSC Adv 3:6369–6376CrossRefGoogle Scholar
  32. Tu WG, Zhou Y, Liu Q, Tian ZP, Gao J, Chen XY, Zhang HT, Liu JG, Zou ZG (2012) Robust hollow spheres consisting of alternating titania nanosheets and graphene nanosheets with high photocatalytic activity for CO2 conversion into renewable fuels. Adv Funct Mater 22:1215–1221CrossRefGoogle Scholar
  33. Wang P, Huang BB, Qin XY, Zhang X, Dai Y, Wei JY, Whangbo MH (2008) Ag@ AgCl: a highly efficient and stable photocatalyst active under visible light. Angew Chem Int Ed 47:7931–7933CrossRefGoogle Scholar
  34. Wu ZC, Xu CR, Wu YQ, Yu H, Tao Y, Wan H, Gao F (2013) ZnO nanorods/Ag nanoparticles heterostructures with tunable Ag contents: a facile solution-phase synthesis and applications in photocatalysis. CrystEngComm 15:5994–6002CrossRefGoogle Scholar
  35. Xiao MD, Jiang RB, Wang F, Fang CH, Wang JF, Yu JC (2013) Plasmon-enhanced chemical reactions. J Mater Chem A 1:5790–5805CrossRefGoogle Scholar
  36. Yan YF, Liu P, Wen JG, To B, Al-Jassim MM (2003) In-situ formation of ZnO nanobelts and metallic Zn nanobelts and nanodisks. J Phys Chem B 107:9701–9704CrossRefGoogle Scholar
  37. Yi ZG, Ye JH, Kikugawa N, Kako T, Ouyang SX, Stuart-Williams H, Yang H, Cao JY, Luo WJ, Li ZS, Liu Y, Withers RL (2010) An orthophosphate semiconductor with photooxidation properties under visible-light irradiation. Nat Mater 9:559–564CrossRefGoogle Scholar
  38. Zhang QH, Han WD, Hong YJ, Yu JG (2009) Photocatalytic reduction of CO2 with H2O on Pt-loaded TiO2 catalyst. Catal Today 148:335–340CrossRefGoogle Scholar
  39. Zhang ZY, Shao CL, Sun YY, Mu JB, Zhang MY, Zhang P, Guo ZC, Liang PP, Wang CH, Liu YC (2012) Tubular nanocomposite catalysts based on size-controlled and highly dispersed silver nanoparticles assembled on electrospun silica nanotubes for catalytic reduction of 4-nitrophenol. J Mater Chem 22:1387–1395CrossRefGoogle Scholar
  40. Zhang XM, Chen YL, Liu RS, Tsai DP (2013) Plasmonic photocatalysis. Rep Prog Phys 76:46401–46442CrossRefGoogle Scholar
  41. Zhao CY, Liu LJ, Zhang QY, Wang J, Li Y (2012) Photocatalytic conversion of CO2 and H2O to fuels by nanostructured Ce-TiO2/SBA-15 composites. Catal Sci Technol 2:2558–2568CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Da Wang
    • 1
    • 2
  • Yan Yu
    • 1
  • Zhipeng Zhang
    • 1
  • Huiying Fang
    • 1
  • Jianmeng Chen
    • 1
  • Zhiqiao He
    • 1
  • Shuang Song
    • 1
    Email author
  1. 1.College of Biological and Environmental EngineeringZhejiang University of TechnologyHangzhouChina
  2. 2.School of Municipal and Environmental EngineeringHarbin Institute of TechnologyHarbinChina

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