铁掺杂纳米羟基磷灰石的制备及紫外吸收性能研究

doi:10.15541/jim20240413

无机材料学报 ›› 2025, Vol. 40 ›› Issue (5): 457-465.DOI: 10.15541/jim20240413

铁掺杂纳米羟基磷灰石的制备及紫外吸收性能研究

安然¹(), 林锶¹, 郭世刚², 张冲², 祝顺², 韩颖超¹()

1.武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
2.山东朱氏药业集团有限公司, 菏泽 274300

收稿日期:2024-09-18 修回日期:2024-12-08 出版日期:2025-05-20 网络出版日期:2024-12-27
通讯作者: 韩颖超, 研究员. E-mail: hanyingchao@whut.edu.cn
作者简介:安然(2000-), 男, 硕士研究生. E-mail: ar17864218908@163.com
基金资助:
山东省发展和改革委员会人才项目

Iron-doped Nano-hydroxyapatite: Preparation and Ultraviolet Absorption Performance

AN Ran¹(), LIN Si¹, GUO Shigang², ZHANG Chong², ZHU Shun², HAN Yingchao¹()

1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2. Shandong Zhushi Pharmaceutical Group Co., Ltd., Heze 274300, China

Received:2024-09-18 Revised:2024-12-08 Published:2025-05-20 Online:2024-12-27
Contact: HAN Yingchao, professor. E-mail: hanyingchao@whut.edu.cn
About author:AN Ran (2000-), male, Master candidate. E-mail: ar17864218908@163.com
Supported by:
Shandong Provincial Development and Reform Commission Talent Program

摘要/Abstract

摘要：

纳米羟基磷灰石(nHAP)兼具生物相容性及环境友好性, 经铁掺杂改性后, 有望作为一种新型紫外(UV)吸收材料。本研究采用共沉淀法和水热法制备了铁掺杂纳米羟基磷灰石(Fe-nHAP), 通过调节反应时间、温度和铁掺杂比探究了制备工艺对UV吸收性能的影响。结果表明, 随着温度从37 ℃升高至150 ℃, 或将反应时间从0.5 h延长至3 h, 材料结晶度及UV吸收峰值均有一定程度的提升, 表明Fe-nHAP的UV吸收性能与结晶度具有正关联。此外, Fe-nHAP的UV吸收性能还与铁掺杂比密切相关。随着铁掺杂摩尔比从0增至10%, Fe-nHAP的UV吸收性能逐渐增强, 最大吸收值从0.03增至1.35, 这归因于铁掺杂引起材料能带结构变化, 进而使其光学带隙缩小。然而, 高掺杂比导致材料结晶度过低, 使得UV吸收性能提升效果减弱。安全性评价表明铁掺杂摩尔比为7%的Fe-nHAP未表现出细胞毒性、光毒性及皮肤刺激性。综上, Fe-nHAP具备较强的UV吸收性能, 加之良好的生物安全性, 有望成为一种新型UV吸收材料。

关键词: 纳米羟基磷灰石, 铁掺杂, 紫外吸收

Abstract:

Nano-hydroxyapatite (nHAP) possesses both biocompatibility and environmental friendliness, and holds the potential to become a novel ultraviolet (UV) absorbent material following iron doping modification. This study employed co-precipitation and hydrothermal methods to prepare iron-doped nano-hydroxyapatite (Fe-nHAP). Influence of the preparation process on UV absorption performance was investigated by adjusting reaction time, temperature, and iron doping ratio. The results indicate that with the increase of temperature from 37 ℃ to 150 ℃ or the extension of reaction time from 0.5 h to 3 h, both the crystallinity and the peak of UV absorption improve. It can be inferred that there is a certain positive correlation between the UV absorption performance and crystallinity of Fe-nHAP. Additionally, the UV absorption capacity is closely correlated to the iron doping ratio. As the iron doping molar ratio increases from 0 to 10%, the UV absorption capacity is gradually enhanced, with the maximum absorption value rising from 0.03 to 1.35. This phenomenon is attributed to the reduction in optical bandgap caused by iron doping. However, a high iron doping ratio leads to excessive reduction in material crystallinity, resulting in weakened enhancement of UV absorption performance. The safety assessment indicates that Fe-nHAP with an iron doping molar ratio of 7% does not demonstrate cytotoxicity, phototoxicity and skin irritation. In summary, Fe-nHAP has a suitable UV absorption performance. With its favorable biosecurity, it is anticipated to emerge as a new type of UV absorption material.

Key words: nano-hydroxyapatite, iron doping, ultraviolet absorption

中图分类号:

TQ174

安然, 林锶, 郭世刚, 张冲, 祝顺, 韩颖超. 铁掺杂纳米羟基磷灰石的制备及紫外吸收性能研究[J]. 无机材料学报, 2025, 40(5): 457-465.

AN Ran, LIN Si, GUO Shigang, ZHANG Chong, ZHU Shun, HAN Yingchao. Iron-doped Nano-hydroxyapatite: Preparation and Ultraviolet Absorption Performance[J]. Journal of Inorganic Materials, 2025, 40(5): 457-465.

图/表 14

图1 Fe-nHAP的XRD图谱

Fig. 1 XRD patterns of as-prepared Fe-nHAP (a) 37-150 ℃, 3 h, 1%Fe-nHAP; (b) 150 ℃, 0.5-3 h, 1%Fe-nHAP; (c) 150 ℃, 3 h, 0-10%Fe

表1 不同反应温度(T)制备的Fe-nHAP的晶格参数、晶胞体积、结晶度和晶粒尺寸

Table 1 Lattice parameters, volumes, crystallinities, and grain sizes of Fe-nHAP prepared under different temperatures (T)

T/℃	a-axis/Å	c-axis/Å	Volume/Å³	Crystallinity/%	D₍₀₀₂₎/nm	D₍₃₁₀₎/nm
37	9.39411	6.80010	525.23	19.56	43.50	20.11
60	9.39522	6.80268	525.54	21.25	49.66	20.30
80	9.39580	6.82520	525.46	25.56	54.33	20.33
100	9.39954	6.84554	526.65	30.77	57.28	21.05
150	9.40185	6.86230	526.90	32.00	61.50	25.49

表2 不同反应时间制备的Fe-nHAP的晶格参数、晶胞体积、结晶度和晶粒尺寸

Table 2 Lattice parameters, volumes, crystallinities, and grain sizes of Fe-nHAP prepared for different time

Time/h	a-axis/Å	c-axis/Å	Volume/Å³	Crystallinity/%	D₍₀₀₂₎/nm	D₍₃₁₀₎/nm
0.5	9.32063	6.77150	525.11	16.77	46.72	23.05
1	9.32145	6.79534	525.45	20.70	49.52	23.21
3	9.32498	6.82841	526.55	32.13	61.08	25.44
5	9.32705	6.83254	526.73	33.06	62.01	25.54

表3 不同Fe掺杂比的Fe-nHAP的晶格参数、晶胞体积、结晶度和晶粒尺寸

Table 3 Lattice parameters, volumes, crystallinities, and grain sizes of Fe-nHAP with Fe doped at different molar ratios

Sample	a-axis/Å	c-axis/Å	Volume/Å³	Crystallinity/%	D₍₀₀₂₎/nm	D₍₃₁₀₎/nm
nHAP	9.33129	6.70756	527.13	43.92	70.79	31.45
0.3%Fe-nHAP	9.33089	6.70422	526.85	38.71	65.22	26.68
1%Fe-nHAP	9.32652	6.70033	526.21	32.04	61.12	25.44
3%Fe-nHAP	9.32421	6.69054	526.06	32.10	60.46	25.29
7%Fe-nHAP	9.32056	6.68135	525.98	30.36	56.23	25.10
10%Fe-nHAP	9.32001	6.68045	525.73	27.77	55.28	25.12

图2 Fe-nHAP(150 ℃、3 h、0~10%Fe)的FT-IR光谱图

Fig. 2 FT-IR spectra of Fe-nHAP (150 ℃, 3 h, 0-10%Fe)

图3 Fe-nHAP(150 ℃、3 h、0~10%Fe)的TEM照片(插图为高分辨TEM(HRTEM)照片)

Fig. 3 TEM images of Fe-nHAP (150 ℃, 3 h, 0-10%Fe) with insets showing corresponding HRTEM images (a) nHAP; (b) 0.3%Fe-nHAP; (c) 1%Fe-nHAP; (d) 3%Fe-nHAP; (e) 7%Fe-nHAP; (f) 10%Fe-nHAP

表4 Fe-nHAP(150 ℃、3 h、0~10%Fe)元素占比(%, 质量分数)

Table 4 Elemental composition (%, mass fraction) of Fe-nHAP (150 ℃, 3 h, 0-10%Fe)

Element	nHAP	0.3%Fe-nHAP	1%Fe-nHAP	3%Fe-nHAP	7%Fe-nHAP	10%Fe-nHAP
Ca	37.11176	38.84537	38.44196	37.46884	34.68688	32.83218
P	17.12133	18.47263	18.33874	18.44668	18.06182	17.50755
Fe	0.00589	0.22444	0.69487	2.04870	4.65011	6.35854

图4 (a)不同反应温度制备的1%Fe-nHAP的UV吸收性能; (b)不同反应时间制备的1%Fe-nHAP的UV吸收性能; (c) 1%Fe-nHAP结晶度与UV吸收性能的关系

Fig. 4 (a) UV absorption performance of 1%Fe-nHAP prepared under different temperatures; (b) UV absorption performance of 1%Fe-nHAP prepared for different time; (c) Relationship between crystallinity and UV absorption performance of 1%Fe-nHAP

图5 (a)不同材料的UV吸收性能; (b)不同铁掺杂比对Fe-nHAP结晶度及UV吸收性能的影响; (c)不同材料的Tauc曲线

Fig. 5 (a) UV absorption performance of different materials; (b) Effect of iron doping ratio on crystallinity and UV absorption performance of Fe-nHAP; (c) Tauc curves of different materials

图6 不同材料的XPS谱图以及UV吸收谱图

Fig. 6 XPS spectra and UV absorption spectra of different materials (a) nHAP; (b) 7%Fe-nHAP; (c) 10%Fe-nHAP; (d) Fine Fe2p orbital spectrum of 7%Fe-nHAP; (e) Fine Fe2p orbital spectrum of 10%Fe-nHAP; (f) UV absorption performance of two valence states of Fe in 7%Fe-nHAP

图7 Fe-nHAP(0~10%Fe)的亲疏水性

Fig. 7 Hydrophobicity of Fe-nHAP (0-10%Fe)

表5 Fe-nHAP的4项重金属和5项菌落数九项测试

Table 5 Test results of Fe-nHAP on 4 heavy metals and 5 microorganisms

Test item	Concentration/ (mg·kg^-1)	Limit/ (mg·kg^-1)
Hg	0.002	1
Pb	0.05	10
As	0.01	2
Cd	0.18	5
Total colony count	-	500
Yeasts and molds count	-	100
T-E. coli	-	0
Staphylococcus aureus	-	0
Pseudomonas aeruginosa	-	0

图8 Fe-nHAP(0~10%Fe)的细胞相容性

Fig. 8 Cell compatibilities of Fe-nHAP (0-10%Fe) (a, b) Cell viability after being cultured for (a) 2 and (b) 4 d at different concentrations; (c) Cell dead/live staining after being cultured at a concentration of 200 μg/mL. Colorful figures are available on website

图9 7% Fe-nHAP样品的皮肤刺激性对比试验

Fig. 9 Skin irritation comparison test of 7%Fe-nHAP (a, b) Before application; (c, d) After 14 d

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铁掺杂纳米羟基磷灰石的制备及紫外吸收性能研究

Iron-doped Nano-hydroxyapatite: Preparation and Ultraviolet Absorption Performance

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