Abstract
Boron-rich semiconductors make significant contributions to the family of explored metal-free photocatalysts, which have attracted much attention in recent years. Boron carbide (B4C) belongs to a typical metal-free boron-rich photocatalyst which is facing difficulties in further optimization mainly due to the extreme conditions required for the synthesis of this material. In the present work, five different transition-metal catalysts (Fe, Co, Ni, Cu, and Zn) were investigated for lowering the crystallization temperature of B4C. Ni is the best catalyst for the reaction, and the crystalline mesoporous B4C powders can be obtained at merely 850 °C with a surface area of 130.55 m2 g−1, which is 27 times larger than commercial B4C. The photocatalytic properties of B4C prepared with Ni catalyst at different calcination temperatures were further evaluated by photocatalytic CO2 reduction and generation of hydroxyl radicals. Both the crystallinity and surface area of the B4C would influence the final photocatalytic properties. For B4C photocatalysts, we firstly found that the crystallinity would influence the photogenerated holes more significantly while the surface area would have more significant influence on the photogenerated electrons. The B4C obtained at 950 °C exhibits the best photocatalytic activities for both CO2 reduction and generation of ·OH radicals, which are 3.1 and 2.1 times higher than the commercial B4C, respectively. This present study may provide crucial references for the low-temperature synthesis of crystalline B4C and new opportunities for the application of the metal-free B4C photocatalysts to solar energy conversion.
Similar content being viewed by others
References
Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor electrode. Nature 238:37
Walter MG, Warren EL, Mckone JR, Boettcher SW, Mi QX, Santori EA, Lewis NS (2010) Solar water splitting cells. Chem Rev 110:6446–6473
Lewis NS (2016) Research opportunities to advance solar energy utilization. Science 351:1920
Kudo A, Miseki Y (2009) Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev 38:253–278
Lewis NS, Nocera DG (2006) Powering the planet: chemical challenges in solar energy utilization. Proc Natl Acad Sci USA 104:15729–15735
Chen R, Pang S, An H, Zhu J, Ye S, Gao Y, Fan F, Li C (2018) Charge separation via asymmetric illumination in photocatalytic Cu2O particles. Nat Energy 3:655–663
Hao WC, Pan F, Wang TM (2005) Photocatalytic activity TiO2 granular films prepared by layer-by-layer self-assembly method. J Mater Sci 40:1251–1253. https://doi.org/10.1007/s10853-005-6945-x
Luo Z, Wang T, Zhang J, Li C, Li H, Gong J (2017) Dendritic hematite nanoarray photoanode modified with a conformal titanium dioxide interlayer for effective charge collection. Angew Chem Int Ed 56:12878–12882
Pei L, Lv B, Wang S, Yu Z, Yan S, Abe R, Zou Z (2018) Oriented growth of Sc-doped Ta3N5 nanorod photoanode achieving low-onset-potential for photoelectrochemical water oxidation. ACS Appl Energy Mater 1:4150–4157
Nie N, Zhang L, Fu J, Cheng B, Yu J (2018) Self-assembled hierarchical direct Z-scheme g-C3N4/ZnO microspheres with enhanced photocatalytic CO2 reduction performance. Appl Surf Sci 441:12–22
Xu H, Wu Z, Wang YT, Lin CS (2017) Enhanced visible-light photocatalytic activity from graphene-like boron nitride anchored on graphitic carbon nitride sheets. J Mater Sci 52:9477–9490. https://doi.org/10.1007/s10853-017-1167-6
Wang Y, Sun MX, Fang YL, Sun SF, He J (2016) Ag2S and MoS2 as dual, co-catalysts for enhanced photocatalytic degradation of organic pollutions over CdS. J Mater Sci 51:779–787. https://doi.org/10.1007/s10853-015-9401-6
Hou Y, Zhu Y, Xu Y, Wang X (2014) Photocatalytic hydrogen production over carbon nitride loaded with WS2 as cocatalyst under visible light. Appl Catal B Environ 156–157:122–127
Guan Z, Luo W, Xu Y, Tao Q, Wen X, Zou Z (2016) Aging precursor solution in high humidity remarkably promoted grain growth in Cu2ZnSnS4 films. ACS Appl Mater Interfaces 8:5432–5438
Wang X, Maeda K, Thomas A, Takanabe K, Xin G, Carlsson JM, Domen K, Antonietti M (2009) A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater 8:76–80
Liu G, Yin L, Niu P, Jiao W, Cheng HM (2013) Visible-light-responsive β-rhombohedral boron photocatalysts. Angew Chem Int Ed 52:6242–6245
Liu G, Meng X, Zhang H et al (2017) Elemental boron for efficient carbon dioxide reduction under light irradiation. Angew Chem Int Ed 56:5570–5574
Liu G, Niu P, Yin L, Cheng HM (2012) α-sulfur crystals as a visible-light-active photocatalyst. J Am Chem Soc 134:9070–9073
Wang F, Ng WKH, Yu JC, Zhu H, Li C, Zhang L, Liu Z, Li Q (2012) Red phosphorus: an elemental photocatalyst for hydrogen formation from water. Appl Catal B Environ 111–112:409–414
Zhu X, Zhang T, Sun Z et al (2017) Black phosphorus revisited: a missing metal-free elemental photocatalyst for visible light hydrogen evolution. Adv Mater 29:1605776
Wang S, Swingle SF, Ye H, Fan FF, Cowley AH, Bard AJ (2012) Synthesis and characterization of a p-type boron arsenide photoelectrode. J Am Chem Soc 134:11056–11059
Shi L, Li P, Zhou W et al (2016) n-Type boron phosphide as a highly stable, metal-free, visible-light-active photocatalyst for hydrogen evolution. Nano Energy 28:158–163
Huang C, Chen C, Zhang M, Lin L, Ye X, Lin S, Antonietti M, Wang X (2015) Carbon-doped BN nanosheets for metal-free photoredox catalysis. Nat Commun 6:7698
Fu Y, Zhu X, Huang L, Zhang X, Zhang F, Zhu W (2018) Azine-based covalent organic frameworks as metal-free visible light photocatalysts for CO2 reduction. Appl Catal B Environ 239:46–51
Liu J, Wen S, Hou Y, Zou F, Beran GO, Feng P (2013) Boron carbides as efficient, metal-free, visible-light-responsive photocatalysts. Angew Chem Int Ed 52:3241–3245
Fang Y, Wang X (2017) Metal-free boron-containing heterogeneous catalysts. Angew Chem Int Ed 56:15506–15518
Zhang X, Yang J, Cai T, Zuo G, Tang C (2018) TiO2 nanosheets decorated with B4C nanoparticles as photocatalysts for solar fuel production under visible light irradiation. Appl Surf Sci 443:558–566
Zhang X, Wang L, Du Q, Wang Z, Ma S, Yu M (2016) Photocatalytic CO2 reduction over B4C/C3N4 with internal electric field under visible light irradiation. J Colloid Interface Sci 464:89–95
Thevenot F (1991) A review on boron carbide. Key Eng Mater 56–57:59–88
Lee JH, Won CW, Joo SM, Maeng DY, Kim HS (2000) Preparation of B4C powder from B2O3 oxide by SHS process. J Mater Sci Lett 19:951–954
Dai H, Wong EW, Lu YZ, Fan S, Lieber CM (1995) Synthesis and characterization of carbide nanorods. Nature 375:769–772
Ma R, Bando Y (2002) Investigation on the growth of boron carbide nanowires. Chem Mater 14:4403–4407
Xu FF, Bando Y (2004) Formation of two-dimensional nanomaterials of boron carbides. J Phys Chem B 108:7651–7655
Tao X, Dong L, Wang X, Zhang W, Nelson BJ, Li X (2010) B4C-nanowires/carbon-microfiber hybrid structures and composites from cotton T-shirts. Adv Mater 22:2055–2059
Guan Z, Gutu T, Yang J, Yang Y, Zinn AA, Li D, Xu TT (2012) Boron carbide nanowires: low temperature synthesis and structural and thermal conductivity characterization. J Mater Chem 22:9853–9860
Gu Y, Chen L, Qian Y, Zhang W, Ma J (2005) Synthesis of nanocrystalline boron carbide via a solvothermal reduction of CCl4 in the presence of amorphous boron powder. J Am Ceram Soc 88:225–227
Wei BQ, Vajtai R, Jung YJ, Banhart F, Ramanath G, Ajayan PM (2002) Massive icosahedral boron carbide crystals. J Phys Chem B 106:5807–5809
Carlsson M, Garcia FJG, Johnsson M (2002) Synthesis and characterisation of boron carbide whiskers and thin elongated platelets. J Cryst Growth 236:466–476
Tao X, Li Y, Du J et al (2011) A generic bamboo-based carbothermal method for preparing carbide (SiC, B4C, TiC, TaC, NbC, TixNb1−xC, and TaxNb1−xC) nanowires. J Mater Chem 21:9095–9102
Yu J, Fan J, Lv K (2010) Anatase TiO2 nanosheets with exposed (001) facets: improved photoelectric conversion efficiency in dye-sensitized solar cells. Nanoscale 2:2144–2149
Salmasi M, Fatemi S, Najafabadi AT (2011) Improvement of light olefins selectivity and catalyst lifetime in MTO reaction; using Ni and Mg-modified SAPO-34 synthesized by combination of two templates. J Ind Eng Chem 17:755–761
Rouquerol J, Avnir D, Fairbridge CW et al (1994) Physical chemistry division commission on colloid and surface chemistry, subcommittee on characterization of porous solids: recommendations for the characterization of porous solids. Pure Appl Chem 66:1739–1758
Hirakawa T, Nosaka Y (2002) Properties of O ·−2 and OH· formed in TiO2 aqueous suspensions by photocatalytic reaction and the influence of H2O2 and some ions. Langmuir 18:3247–3254
Cermignani W, Paulson TE, Onneby C, Pantano CG (1995) Synthesis and characterization of boron-doped carbons. Carbon 33:367–374
Wang H, Guo Q, Yang J et al (2013) Microstructure and thermophysical properties of B4C/graphite composites containing substitutional boron. Carbon 52:10–16
Ronning C, Schwen D, Eyhusen S, Vetter U, Hofsäss H (2002) Ion beam synthesis of boron carbide thin films. Surf Coat Technol 158–159:382–387
Jiménez I, Sutherland DGJ, Buuren T, Carlisle JA, Terminello LJ, Himpsel FJ (1998) Photoemission and x-ray-absorption study of boron carbide and its surface thermal stability. Phys Rev B 57:13167–13174
Chen R, Shi Q, Su L et al (2017) Preparation of a B4C hollow microsphere through gel-casting for an inertial confinement fusion (ICF) target. Ceram Int 43:571–577
Werheit H (2006) On excitons and other gap states in boron carbide. J Phys Condens Matter 18:10655–10662
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (21506183) and the foundation by Hunan 2011 Collaborative Innovation Center of Chemical Engineering & Technology with Environmental Benignity and Effective Resource Utilization.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Yan, D., Liu, J., Fu, X. et al. Low-temperature synthesis of mesoporous boron carbides as metal-free photocatalysts for enhanced CO2 reduction and generation of hydroxyl radicals. J Mater Sci 54, 6151–6163 (2019). https://doi.org/10.1007/s10853-018-03284-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-018-03284-9