采用水热法制备短棒状羟基磷灰石(HA),通过液相剥离法制备黑磷烯(black phosphorene, BP),并采用不同的离心速率分离出具有不同尺寸的BP。制备BP质量分数为7.0%的BP/HA混合物,用X射线衍射仪、扫描电镜、透射电镜、原子力显微镜和拉曼光谱对混合物的物相组成、微观形貌和结构进行表征,同时使用气体传感系统研究纯HA以及含有不同尺寸BP的BP/HA混合物的气体传感特性。结果表明,加入BP可显著提高HA对氨气的响应,BP的尺寸越小,对HA气敏性能的提升越大。其中BP-10000/HA对浓度(气敏实验所用空气中氨气的体积分数)为100×10-6的氨气的响应高达58.7%,当氨气浓度上升到1 000×10-6后,响应高达98.3%。BP尺寸越小,气敏性能越好,可能是由于具有更大的比表面积,因而具备更多的活性位点。总之,BP可显著提升HA的气敏性能,BP/HA混合物是一种很有前途的室温气敏材料。
In this work, rod-shaped hydroxyapatite (HA) was prepared by hydrothermal method, and black phosphorene (BP) with different sizes was prepared by liquid-phase exfoliation and separated by adopting different centrifugation speed. BP/HA hybrid was prepared with BP at 7.0% mass fraction. The phase composition, micro-morphology and structure of BP/HA were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, atomic force microscopy and Raman spectroscopy. The gas sensing properties of pure HA and BP/HA with different sizes of BP were investigated using a gas sensing system. The results show that the addition of BP significantly improves the response of HA to ammonia, and the gas-sensing performance of HA is improved the most with the addition of BP with smaller size. Among them, the response of BP-10000/HA to the ammonia concentration of 100×10-6 is as high as 58.7%, and when the ammonia concentration isincreased to 1 000×10-6, the response is as high as 98.3%. The smaller the size of BP, the better the gas sensing performance may be due to its larger specific surface area and thus more active sites. In conclusion, BP can significantly improve the gas sensitivity of HA, and BP/HA is a promising gas sensitive material at room temperature.
[1] NAGAI M, NISHINO T, SAEKI T.A new type of CO2 gas sensor comprising porous hydroxyapatite ceramics[J]. Sensors and Actuators, 1988, 15(2): 145-151.
[2] MAHABOLE M P, MENE R U, KHAIRNAR R S.Gas sensing and dielectric studies on cobalt doped hydroxyapatite thick films[J]. Advanced Materials Letters, 2013, 4(1): 46-52.
[3] MENE R U, MAHABOLE M P, MOHITE K C, et al.Improved gas sensing and dielectric properties of Fe doped hydroxyapatite thick films: Effect of molar concentrations[J]. Materials Research Bulletin, 2014, 50: 227-234.
[4] MENE R U, MAHABOLE M P, MOHITE K C, et al.Fe doped hydroxyapatite thick films modified via swift heavy ion irradiation for CO and CO2 gas sensing application[J]. Journal of Alloys and Compounds, 2014, 584: 487-493.
[5] ANJUM S R, KHAIRNAR R S.Integrated sensing of alcohols by CNT blended HAP nano ceramics sensors[J]. Sensors & Transducers, 2016, 206(11): 1-7.
[6] ANJUM S R, KHAIRNAR R S.Carbon nanotubes blended hydroxyapatite ethanol sensor[J]. Sensing and Imaging, 2016, 17(1): 18-25.
[7] TAHA S, BEGUM S, NARWADE V N, et al.Development of alcohol sensor using TiO2-Hydroxyapatite nano-composites[J]. Materials Chemistry and Physics, 2020, 240: 122228.
[8] ANJUM S R, NARWADE V N, BOGLE K A, et al.Graphite doped hydroxyapatite nanoceramic: Selective alcohol sensor[J]. Nano-Structures and Nano-Objects, 2018, 14: 98-105.
[9] LI H X, LIU Y, TAN Y N, et al.Room temperature gas sensing properties of tubular hydroxyapatite[J]. New Journal of Chemistry, 2015, 39(5): 3865-3874.
[10] LI H X, LIU Y, Luo L L, et al.Development of ammonia sensors by using conductive polymer/hydroxyapatite composite materials[J]. Materials Science and Engineering C, 2016, 59: 438-444.
[11] 罗兰兰. 羟基磷灰石复合物的制备及其气敏性能研究[D]. 长沙: 中南大学, 2015.
LUO Lanlan.Research on the synthesis of hydroxyapatite composites and its gas sensing property[D]. Changsha: Central South University, 2015.
[12] TAN Y N, LI H X, LIU Y, et al.Acidithiobacillus ferrooxidans improved H2S gas sensing properties of tubular hydroxyapatite at room temperature[J]. RSC Advances, 2016, 6(80): 76874-76878.
[13] ZHANG Q, LIU Y, ZHANG Y, et al.Facile and controllable synthesis of hydroxyapatite/graphene hybrid materials with enhanced sensing performance towards ammonia[J]. Analyst, 2015, 140(15): 5235-5242.
[14] DONARELLI M, OTTAVIANO L.2D materials for gas sensing applications: A review on graphene oxide, MoS2, WS2 and Phosphorene[J]. Sensors, 2018, 18(11): 3638.
[15] KOU L, FRAUENHEIM T, CHEN C.Phosphorene as a superior gas sensor: Selective adsorption and distinct I-V response[J]. The Journal of Physical Chemistry Letters, 2014, 5(15): 2675-2681.
[16] CHO S Y, LEE Y, KOH H J, et al.Superior chemical sensing performance of black phosphorus: Comparison with MoS2 and graphene[J]. Advanced Materials, 2016, 28(32): 7020-7028.
[17] PUMERA M.Phosphorene and black phosphorus for sensing and biosensing[J]. Trac-trends in Analytical Chemistry, 2017, 93: 1-6.
[18] WANG Y, XUE J, ZHANG X, et al.Novel intercalated CuO/black phosphorus nanocomposites: Fabrication, characterization and NO2 gas sensing at room temperature[J]. Materials Science in Semiconductor Processing, 2020, 110: 104961.
[19] LI Q, CEN Y, HUANG J Y, et al.Zinc oxide-black phosphorus composites for ultrasensitive nitrogen dioxide sensing[J]. Nanoscale Horizons, 2018, 3(5): 525-531.
[20] WANG Y, ZHOU Y, REN H, et al.Room-temperature and humidity-resistant trace nitrogen dioxide sensing of few-layer black phosphorus nanosheet by incorporating zinc oxide nanowire[J]. Analytical Chemistry, 2020, 92(16): 11007-11017.
[21] LIU Z H, HUANG J Y, WANG Q, et al.Indium oxide-black phosphorus composites for ultrasensitive nitrogen dioxide sensing at room temperature[J]. Sensors and Actuators B: Chemical, 2020, 308: 127650.
[22] CUI S M, PU H H, WELLS S A, et al.Ultrahigh sensitivity and layer-dependent sensing performance of phosphorene-based gas sensors[J]. Nature Communications, 2015, 6(1): 8632.
[23] CHEN T D, CHENG Z Q, TIAN Q, et al.Nitrogen dioxide gas sensor based on liquid-phase-exfoliated black phosphorus nanosheets[J]. ACS Applied Nano Materials, 2020, 3(7): 6440-6447.
[24] CHEN Y N, LI M L, LI Y P, et al.Hydroxyapatite modified sludge-based biochar for the adsorption of Cu2+ and Cd2+: Adsorption behavior and mechanisms[J]. Bioresource Technology, 2021, 321: 124413.
[25] 张青. 羟基磷灰石—石墨烯复合物的制备及其气敏性能研究[D]. 长沙: 中南大学, 2014.
ZHAGN Qing.Research on the synthesis of hydroxyapatite- graphenecomposites and its gas sensing property[D]. Changsha: Central South University, 2014.
[26] PANG Y X, BAO X.Influence of temperature, ripening time and calcination on the morphology and crystallinity of hydroxyapatite nanoparticles[J]. Journal of the European Ceramic Society, 2003, 23(10): 1697-1704.
[27] PRASONGKIT J, SHUKLA V, GRIGORIEV A, et al.Ultrahigh-sensitive gas sensors based on doped phosphorene: A first-principles investigation[J]. Applied Srface Science, 2019, 497: 143660.
[28] ZHANG X, XIE H M, LIU Z D, et al.Black phosphorus quantum dots[J]. Angewandte Chemie-International Edition, 2015, 54(12): 3653-3657.
[29] ALSAFFAR F, ALODAN S, ALRASHEED A, et al.Raman sensitive degradation and etching dynamics of exfoliated black phosphorus[J]. Scientific Reports, 2017, 7: 44540.
[30] GUO Z N, ZHANG H, LU S B, et al.From black phosphorus to phosphorene: basic solvent exfoliation, evolution of Raman scattering, and applications to ultrafast photonics[J]. Advanced Functional Materials, 2015, 25(45): 6996-7002.
[31] 李会霞. 管状羟基磷灰石及其复合物的制备与气敏性能研究[D]. 长沙: 中南大学, 2016.
LI Huixia.Synthesis and gas sensing properties of tubularhydroxyapatite and its composites[D]. Changsha: Central South University, 2016.
