Citation: WANG Kexin, SHI Liurong, WANG Mingzhan, YANG Hao, LIU Zhongfan, PENG Hailin. Biomass Hydroxyapatite-templated Synthesis of 3D Graphene[J]. Acta Physico-Chimica Sinica, ;2019, 35(10): 1112-1118. doi: 10.3866/PKU.WHXB201805032 shu

Biomass Hydroxyapatite-templated Synthesis of 3D Graphene

WANG Kexin ¹ ,
SHI Liurong ¹ ,
WANG Mingzhan ¹ ,
YANG Hao ² ,
LIU Zhongfan ^1,3,, ,
PENG Hailin ^1,3,,

1.
Center for Nanochemistry (CNC), Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
2.
Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, P. R. China
3.
Beijing Graphene Institute (BGI), Beijing 100095, P. R. China

Corresponding author: LIU Zhongfan, zfliu@pku.edu.cn PENG Hailin, hlpeng@pku.edu.cn
Received Date: 14 May 2018
Revised Date: 22 June 2018
Accepted Date: 26 June 2018
Available Online: 26 October 2018
Fund Project: The project was supported by the Beijing Municipal Science & Technology Commission, China (Z161100002116002, Z161100002116021), the National Basic Research Program of China (2014CB932500, 2016YFA0200101), and the National Natural Science Foundation of China (21525310, 51432002, 51520105003)the National Basic Research Program of China 2014CB932500the National Basic Research Program of China 2016YFA0200101the National Natural Science Foundation of China 21525310the National Natural Science Foundation of China 51432002the Beijing Municipal Science & Technology Commission, China Z161100002116002, Z161100002116021the National Natural Science Foundation of China 51520105003the Beijing Municipal Science & Technology Commission, China Z161100002116002

As a new 2D material with excellent chemical stability, good electric conductivity, and high specific surface area, graphene has been widely used in energy storage and conversion devices. However, 2D graphene layers are easily stacked, which may significantly reduce the surface area and degrade the excellent electrical properties of graphene. To avoid this, one of the most effective methods is to construct 3D graphene (3DG) with specific porous microstructures. Chemical vapor deposition (CVD) is an important method for the synthesis of high-quality 3DG, where templates play a defining role in controlling the structure and cost of 3DG. Metallic materials with 3D microstructures, such as nickel foam, have proven to be useful as substrates for the growth of high-quality 3DG. However, metal substrates are usually expensive, and the pickling solution generated after etching may cause environmental problems. Therefore, non-metallic substrate materials with lower costs have been investigated for the preparation of 3DG. Herein, we developed a novel template material, mammal bone ashes, for the CVD preparation of 3DG. Mammal bone ash is an inexpensive and abundant biomass hydroxyapatite. During the high-temperature CVD reaction, the bone ash powders were slightly sintered to form a continuous porous structure with graphene coating. The morphology of 3DG is inherited from the microstructure of bone ash templates. After removing the bone ash template with hydrochloric acid, the template-grown 3DG was obtained with a unique bicontinuous structure, i.e. both the graphene framework and the void space were continuous. In addition, the pickling solution of the bone ash templates after etching was exactly the same as that for the raw materials for the production of phosphoric acid to achieve high atom utilization. We further optimized the graphitization degrees, layer number, and porous morphology of 3DGs. The microstructure evolution of 3DG is highly relevant to the layer thickness and uniformity of graphene layers. A short growth time would lead to a non-uniform and thin layer of graphene, which is not able to support a complex 3D porous structure. In contrast, a uniform graphene layer with proper thickness is capable of forming a robust 3D architecture. In addition, the facile CVD method can be extended to a series of metal phosphate templates, including tricalcium phosphate [Ca₃(PO₄)₂], trimagnesium phosphate [Mg₃(PO₄)₂], and aluminum phosphate [AlPO₄]. 3DG with bicontinuous morphology is promising as a conductive frame material in electrochemical energy storage devices. As an illustration, high-performance Li-S batteries were fabricated by the uniform composition of an S cathode on 3DG. In comparison with heavily stacked 2D graphene sheets in reduced graphene oxide / S composite, the non-flat structure of 3DGs remained unchanged even after the harsh melt-diffusion process of high-viscosity liquid sulfur. The resulting 3DG/S cathode delivered a high specific capacity of ~550 mAh∙g^-1 at a high current rate (2C). Our work opens an avenue to the low-cost and high-utility production of 3D graphene, which could be integrated with the well-developed phosphorus chemical industry.
- 3D graphene,
- Chemical vapor deposition,
- Bio-waste,
- Hydroxyapatite,
- Li-S battery
1. [1]
  Raccichini, R.; Varzi, A.; Passerini, S.; Scrosati, B. Nat. Mater. 2014, 14 (3), 271. doi: 10.1038/nmat4170 doi: 10.1038/nmat4170
2. [2]
  El-Kady, M. F.; Shao, Y.; Kaner, R. B. Nat. Rev. Mater. 2016, 16033. doi: 10.1038/natrevmats.2016.33 doi: 10.1038/natrevmats.2016.33
3. [3]
  Yang, Z.; Ren, J.; Zhang, Z.; Chen, X.; Guan, G.; Qiu, L.; Zhang, Y.; Peng, H. Chem. Rev. 2015, 115 (11), 5159. doi: 10.1021/cr5006217 doi: 10.1021/cr5006217
4. [4]
  Raccichini, R.; Varzi, A.; Wei, D.; Passerini, S. Adv. Mater. 2017, 29 (11), 1603421. doi: 10.1002/adma.201603421 doi: 10.1002/adma.201603421
5. [5]
  Dong, Y.; Wu, Z. S.; Ren, W.; Cheng, H. M.; Bao, X. Sci. Bull. 2017, 62 (10), 724. doi: 10.1016/j.scib.2017.04.010 doi: 10.1016/j.scib.2017.04.010
6. [6]
  Chen, K.; Chai, Z.; Li, C.; Shi, L.; Liu, M.; Xie, Q.; Zhang, Y.; Xu, D.; Manivannan, A.; Liu, Z. ACS Nano 2016, 10 (3), 3665. doi: 10.1021/acsnano.6b00113 doi: 10.1021/acsnano.6b00113
7. [7]
  Compton, O. C.; Nguyen, S. T. Small 2010, 6 (6), 711. doi: 10.1002/smll.200901934 doi: 10.1002/smll.200901934
8. [8]
  Chen, Z.; Ren, W.; Gao, L.; Liu, B.; Pei, S.; Cheng, H. M. Nat. Mater. 2011, 10 (6), 424. doi: 10.1038/nmat3001 doi: 10.1038/nmat3001
9. [9]
  Cui, C.; Qian, W.; Yu, Y.; Kong, C.; Yu, B.; Xiang, L.; Wei, F. J. Am. Chem. Soc. 2014, 136 (6), 2256. doi: 10.1021/ja412219r doi: 10.1021/ja412219r
10. [10]
  Rümmeli, M. H.; Bachmatiuk, A.; Scott, A.; Börrnert, F.; Warner, J. H.; Hoffman, V.; Lin, J. H.; Cuniberti, G.; Büchner, B. ACS Nano 2010, 4 (7), 4206. doi: 10.1021/nn100971s doi: 10.1021/nn100971s
11. [11]
  Tang, C.; Li, B. Q.; Zhang, Q.; Zhu, L.; Wang, H. F.; Shi, J. L.; Wei, F. Adv. Funct. Mater. 2016, 26 (4), 577. doi: 10.1002/adfm.201503726 doi: 10.1002/adfm.201503726
12. [12]
  Bi, H.; Lin, T.; Xu, F.; Tang, Y.; Liu, Z.; Huang, F. Nano Lett. 2016, 16 (1), 349. doi: 10.1021/acs.nanolett.5b03923 doi: 10.1021/acs.nanolett.5b03923
13. [13]
  Shi, L.; Chen, K.; Du, R.; Bachmatiuk, A.; Rümmeli, M. H.; Priydarshi, M. K.; Zhang, Y.; Manivannan, A.; Liu, Z. Small 2015, 11 (47), 6302. doi: 10.1002/smll.201502013 doi: 10.1002/smll.201502013
14. [14]
  Chen, K.; Li, C.; Shi, L.; Gao, T.; Song, X.; Bachmatiuk, A.; Zou, Z.; Deng, B.; Ji, Q.; Ma, D.; et al. Nat. Commun. 2016, 7, 13440. doi: 10.1038/ncomms13440 doi: 10.1038/ncomms13440
15. [15]
  Shi, L.; Chen, K.; Du, R.; Bachmatiuk, A.; Rümmeli, M. H.; Xie, K.; Huang, Y.; Zhang, Y.; Liu, Z. J. Am. Chem. Soc. 2016, 138 (20), 6360. doi: 10.1021/jacs.6b02262 doi: 10.1021/jacs.6b02262
16. [16]
  Ning, G.; Fan, Z.; Wang, G.; Gao, J.; Qian, W.; Wei, F. Chem. Commun. 2011, 47 (21), 5976. doi: 10.1039/c1cc11159k doi: 10.1039/c1cc11159k
17. [17]
  Zhao, M. Q.; Zhang, Q.; Huang, J. Q.; Tian, G. L.; Nie, J. Q.; Peng, H. J.; Wei, F. Nat. Commun. 2014, 5. doi: 10.1038/ncomms4410 doi: 10.1038/ncomms4410
18. [18]
  Barakat, N. A. M.; Khil, M. S.; Omran, A. M.; Sheikh, F. A.; Kim, H. Y. J. Mater. Process. Tech. 2009, 209 (7), 3408. doi: 10.1016/j.jmatprotec.2008.07.040 doi: 10.1016/j.jmatprotec.2008.07.040
19. [19]
  Sobczak, A.; Kowalski, Z.; Wzorek, Z. Acta. Bioeng. Biomech. 2009, 11 (4), 23.
20. [20]
  Lv, W.; Tang, D. M.; He, Y. B.; You, C. H.; Shi, Z. Q.; Chen, X. C.; Chen, C. M.; Hou, P. X.; Liu, C.; Yang, Q. H. ACS Nano 2009, 3 (11), 3730. doi: 10.1021/nn900933u doi: 10.1021/nn900933u
21. [21]
  Manthiram, A.; Fu, Y.; Chung, S. H.; Zu, C.; Su, Y. S. Chem. Rev. 2014, 114 (23), 11751. doi: 10.1021/cr500062v doi: 10.1021/cr500062v
22. [22]
  Seh, Z. W.; Sun, Y.; Zhang, Q.; Cui, Y. Chem. Soc. Rev. 2016, 45 (20), 5605. doi: 10.1039/C5CS00410A doi: 10.1039/C5CS00410A
23. [23]
  Ji, X.; Nazar, L. F. J. Mater. Chem. 2010, 20 (44), 9821. doi: 10.1039/B925751A doi: 10.1039/B925751A
24. [24]
  Fang, X.; Peng, H. Small 2015, 11 (13), 1488. doi: 10.1002/smll.201402354 doi: 10.1002/smll.201402354
1. [1]
  Yu ZHANG , Fangfang ZHAO , Cong PAN , Peng WANG , Liangming WEI . Application of double-side modified separator with hollow carbon material in high-performance Li-S battery. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1218-1232. doi: 10.11862/CJIC.20230412
2. [2]
  Yan Wang , Jiaqi Zhang , Xiaofeng Wu , Sibo Wang , Masakazu Anpo , Yuanxing Fang . Elucidating oxygen evolution and reduction mechanisms in nitrogen-doped carbon-based photocatalysts. Chinese Chemical Letters, 2025, 36(2): 110439-. doi: 10.1016/j.cclet.2024.110439
3. [3]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
4. [4]
  Ruiqing LIU , Wenxiu LIU , Kun XIE , Yiran LIU , Hui CHENG , Xiaoyu WANG , Chenxu TIAN , Xiujing LIN , Xiaomiao FENG . Three-dimensional porous titanium nitride as a highly efficient sulfur host. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 867-876. doi: 10.11862/CJIC.20230441
5. [5]
  Mengfei He , Chao Chen , Yue Tang , Si Meng , Zunfa Wang , Liyu Wang , Jiabao Xing , Xinyu Zhang , Jiahui Huang , Jiangbo Lu , Hongmei Jing , Xiangyu Liu , Hua Xu . Epitaxial Growth of Nonlayered 2D MnTe Nanosheets with Thickness-Tunable Conduction for p-Type Field Effect Transistor and Superior Contact Electrode. Acta Physico-Chimica Sinica, 2025, 41(2): 100016-. doi: 10.3866/PKU.WHXB202310029
6. [6]
  Huanyan Liu , Jiajun Long , Hua Yu , Shichao Zhang , Wenbo Liu . Rational design of highly conductive and stable 3D flexible composite current collector for high performance lithium-ion battery electrodes. Chinese Chemical Letters, 2025, 36(3): 109712-. doi: 10.1016/j.cclet.2024.109712
7. [7]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
8. [8]
  Yue Li , Minghao Fan , Conghui Wang , Yanxun Li , Xiang Yu , Jun Ding , Lei Yan , Lele Qiu , Yongcai Zhang , Longlu Wang . 3D layer-by-layer amorphous MoS_x assembled from [Mo₃S₁₃]^2- clusters for efficient removal of tetracycline: Synergy of adsorption and photo-assisted PMS activation. Chinese Chemical Letters, 2024, 35(9): 109764-. doi: 10.1016/j.cclet.2024.109764
9. [9]
  Hengying Xiang , Nanping Deng , Lu Gao , Wen Yu , Bowen Cheng , Weimin Kang . 3D core-shell nanofibers framework and functional ceramic nanoparticles synergistically reinforced composite polymer electrolytes for high-performance all-solid-state lithium metal battery. Chinese Chemical Letters, 2024, 35(8): 109182-. doi: 10.1016/j.cclet.2023.109182
10. [10]
  Caili Yang , Tao Long , Ruotong Li , Chunyang Wu , Yuan-Li Ding . Pseudocapacitance dominated Li₃VO₄ encapsulated in N-doped graphene via 2D nanospace confined synthesis for superior lithium ion capacitors. Chinese Chemical Letters, 2025, 36(2): 109675-. doi: 10.1016/j.cclet.2024.109675
11. [11]
  Zhiyuan TONG , Ziyuan LI , Ke ZHANG . Three-dimensional porous collector based on Cu-Li_6.4La₃Zr_1.4Ta_0.6O₁₂ composite layer for the construction of stable lithium metal anode. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 499-508. doi: 10.11862/CJIC.20240238
12. [12]
  Yuexi Guo , Zhaoyang Li , Jingwei Dai . Charlie and the 3D Printing Chocolate Factory. University Chemistry, 2024, 39(9): 235-242. doi: 10.3866/PKU.DXHX202309067
13. [13]
  Hengyi ZHU , Liyun JU , Haoyue ZHANG , Jiaxin DU , Yutong XIE , Li SONG , Yachao JIN , Mingdao ZHANG . Efficient regeneration of waste LiNi_0.5Co_0.2Mn_0.3O₂ cathode toward high-performance Li-ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 625-638. doi: 10.11862/CJIC.20240358
14. [14]
  Rui Li , Ruijie Lu , Libin Yang , Jianwen Li , Zige Guo , Qiquan Yan , Mengjun Li , Yazhuo Ni , Keying Chen , Yaoyang Li , Bo Xu , Mengzhen Cui , Zhan Li , Zhiying Zhao . Immobilization of chitosan nano-hydroxyapatite alendronate composite microspheres on polyetheretherketone surface to enhance osseointegration by inhibiting osteoclastogenesis and promoting osteogenesis. Chinese Chemical Letters, 2025, 36(4): 110242-. doi: 10.1016/j.cclet.2024.110242
15. [15]
  Mingjiao Lu , Zhixing Wang , Gui Luo , Huajun Guo , Xinhai Li , Guochun Yan , Qihou Li , Xianglin Li , Ding Wang , Jiexi Wang . Boosting the performance of LiNi_0.90Co_0.06Mn_0.04O₂ electrode by uniform Li₃PO₄ coating via atomic layer deposition. Chinese Chemical Letters, 2024, 35(5): 108638-. doi: 10.1016/j.cclet.2023.108638
16. [16]
  Xi Xu , Chaokai Zhu , Leiqing Cao , Zhuozhao Wu , Cao Guan . Experiential Education and 3D-Printed Alloys: Innovative Exploration and Student Development. University Chemistry, 2024, 39(2): 347-357. doi: 10.3866/PKU.DXHX202308039
17. [17]
  Qiang Zhou , Pingping Zhu , Wei Shao , Wanqun Hu , Xuan Lei , Haiyang Yang . Innovative Experimental Teaching Design for 3D Printing High-Strength Hydrogel Experiments. University Chemistry, 2024, 39(6): 264-270. doi: 10.3866/PKU.DXHX202310064
18. [18]
  Chengmin Hu , Pingxuan Liu , Ziyang Song , Yaokang Lv , Hui Duan , Li Xie , Ling Miao , Mingxian Liu , Lihua Gan . Tailor-made overstable 3D carbon superstructures towards efficient zinc-ion storage. Chinese Chemical Letters, 2025, 36(4): 110381-. doi: 10.1016/j.cclet.2024.110381
19. [19]
  Xiao-Hong Yi , Chong-Chen Wang . Metal-organic frameworks on 3D interconnected macroporous sponge foams for large-scale water decontamination: A mini review. Chinese Chemical Letters, 2024, 35(5): 109094-. doi: 10.1016/j.cclet.2023.109094
20. [20]
  Yi Zhu , Jingyan Zhang , Yuchao Zhang , Ying Chen , Guanghui An , Ren Liu . Designing unimolecular photoinitiator by installing NHPI esters along the TX backbone for acrylate photopolymerization and their applications in coatings and 3D printing. Chinese Chemical Letters, 2024, 35(7): 109573-. doi: 10.1016/j.cclet.2024.109573

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(625)
HTML views(43)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142