Citation: Wei Liu, Yu-Jing Liu, Liao Chen, Tao Ye, Hong-Zheng Chen, Han-Ying Li. Gel-incorporated PbS and PbI₂ single-crystals[J]. Chinese Chemical Letters, ;2015, 26(5): 504-508. doi: 10.1016/j.cclet.2015.01.020 shu

Gel-incorporated PbS and PbI₂ single-crystals

1.
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, State Key Laboratory of Silicon Materials, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding author: Han-Ying Li,
Received Date: 22 January 2014
Available Online: 9 January 2015
Fund Project: This work was supported by Zhejiang Province Natural Science Foundation (No. LZ13E030002) (No. LZ13E030002) the 973 Program ([56_TD$DIF]No. 2014CB643503) ([56_TD$DIF]No. 2014CB643503) the National Natural Science Foundation of China (Nos. 51222302, 51373150, 51461165301) (Nos. 51222302, 51373150, 51461165301)

Gel-incorporated single-crystals provide unique combinational properties of long-range order and composite structures, which is desired for semiconducting and conducting materials. However, the reported gel-incorporated single-crystals are limited to insulating crystals. Here, we examine crystals of two typical semiconductors, lead sulfide (PbS) and lead iodide (PbI₂), grown from both silica gels and agarose gels. In all the four crystal-gel pairs, single-crystals of the cubic phase of PbS and the hexagonal phase of PbI₂ were obtained according to the X-ray diffraction analysis. Dissolution of the gel-grown crystals exposed insoluble materials with the shape similar to the original crystals, indicative of gelincorporation inside the crystals. As such, this work creates a facile strategy to construct 3D heterostructures inside semiconducting single-crystals without destroying their long-range order.
- Single crystals,
- Gel-incorporation,
- Semiconductor,
- PbS,
- PbI₂
1. [1]
  [1] H.K. Henisch, Crystals in Gels and Liesegang Rings, Cambridge University Press, Cambridge, 2005.
2. [2]
  [2] W. Brenner, Z.V.I. Blank, Y. Okamoto, Growth of single crystals of lead sulphide in silica gels near ambient temperatures, Nature 212 (1966) 392-393.
3. [3]
  [3] A.R. Patel, A.V. Rao, Crystal growth in gel media, Bull. Mater. Sci. 4 (1982) 527- 548.
4. [4]
  [4] J.M. García-Ruíz, Growth history of PbS single crystals at room temperature, J. Cryst. Growth 75 (1986) 441-453.
5. [5]
  [5] J.A. Gavira, J.M. García-Ruiz, Agarose as crystallisation media for proteins II: trapping of gel fibres into the crystals, Acta Crystallogr. Sect. D: Biol. Crystallogr. 58 (2002) 1653-1656.
6. [6]
  [6] E. Asenath-Smith, H.Y. Li, E.C. Keene, Z.W. Seh, L.A. Estroff, Crystal growth of calcium carbonate in hydrogels as a model of biomineralization, Adv. Funct. Mater. 22 (2012) 2891-2914.
7. [7]
  [7] H. Nickl, H. Henisch, Growth of calcite crystals in gels, J. Electrochem. Soc. 116 (1969) 1258-1260.
8. [8]
  [8] J.A. Gavira, A.E. Van Driessche, J.-M. Garcia-Ruiz, Growth of ultrastable protein- silica composite crystals, Cryst. Growth Des. 13 (2013) 2522-2529.
9. [9]
  [9] J.M. García-Ruiz, J.A. Gavira, F. Otálora, A. Guasch, M. Coll, Reinforced protein crystals, Mater. Res. Bull. 33 (1998) 1593-1598.
10. [10]
  [10] Y.-X. Huang, J. Buder, R. Cardoso-Gil, et al., Shape development and structure of a complex (Otoconia-Like?) calcite-gelatine composite, Angew. Chem. Int. Ed. 47 (2008) 8280-8284.
11. [11]
  [11] O. Grassmann, R.B. Neder, A. Putnis, P. Löbmann, Biomimetic control of crystal assembly by growth in an organic hydrogel network, Am. Mineral. 88 (2003) 647-652.
12. [12]
  [12] Y.J. Liu, W. Yuan, Y. Shi, et al., Functionalizing single crystals: incorporation of nanoparticles inside gel-grown calcite crystals, Angew. Chem. Int. Ed. Engl. 53 (2014) 4127-4131.
13. [13]
  [13] H.Y. Li, Y. Fujiki, K. Sada, L.A. Estroff, Gel incorporation inside of organic single crystals grown in agarose hydrogels, CrystEngComm 13 (2011) 1060-1062.
14. [14]
  [14] H.Y. Li, H.L. Xin, D.A. Muller, L.A. Estroff, Visualizing the 3D internal structure of calcite single crystals grown in agarose hydrogels, Science 326 (2009) 1244-1247.
15. [15]
  [15] Y. Oaki, S. Hayashi, H. Imai, A hierarchical self-similar structure of oriented calcite with association of an agar gel matrix: inheritance of crystal habit from nanoscale, Chem. Commun. (2007) 2841-2843.
16. [16]
  [16] Y.-Y. Kim, A.S. Schenk, D. Walsh, et al., Bio-inspired formation of functional calcite/metal oxide nanoparticle composites, Nanoscale 6 (2014) 852-859.
17. [17]
  [17] S. Bag, P.N. Trikalitis, P.J. Chupas, G.S. Armatas, M.G. Kanatzidis, Porous semiconducting gels and aerogels from chalcogenide clusters, Science 317 (2007) 490- 493.
18. [18]
  [18] R.I. Petrova, J.A. Swift, Habit changes of sodium bromate crystals grown from gel media, Cryst. Growth Des. 2 (2002) 573-578.
19. [19]
  [19] L. Chen, T. Ye, Y.J. Liu, et al., Gel network incorporation into single-crystals: effects of gel structures and crystal-gel interaction, CrystEngComm 16 (2014) 6901-6906.
20. [20]
  [20] Y.J. Liu, L. Chen, W. Liu, et al., Synthetic polymer/single-crystal composite, Polym. Adv. Technol. 25 (2014) 1189-1194.
21. [21]
  [21] E.J. Crossland, N. Noel, V. Sivaram, et al., Mesoporous TiO₂ single crystals delivering enhanced mobility and optoelectronic device performance, Nature 495 (2013) 215-219.
22. [22]
  [22] R. Zeis, T. Lei, K. Sieradzki, J. Snyder, J. Erlebacher, Catalytic reduction of oxygen and hydrogen peroxide by nanoporous gold, J. Catal. 253 (2008) 132-138.
23. [23]
  [23] Y. Ding, M.W. Chen, J. Erlebacher, Metallic mesoporous nanocomposites for electrocatalysis, J. Am. Chem. Soc. 126 (2004) 6876-6877.
24. [24]
  [24] T. Fujita, P. Guan, K. McKenna, et al., Atomic origins of the high catalytic activity of nanoporous gold, Nat. Mater. 11 (2012) 775-780.
25. [25]
  [25] J.L. Machol, F.W. Wise, R.C. Patel, D.B. Tanner, Vibronic quantum beats in PbS microcrystallites, Phys. Rev. B 48 (1993) 2819-2822.
26. [26]
  [26] W.H. Song, C.H. Wu, H.Z. Yin, et al., Preparation of PbS nanoparticles by phasetransfer method and application to Pb²⁺-selective electrode based on PVC membrane, Anal. Lett. 41 (2008) 2844-2859.
27. [27]
  [27] B.-R. Hyun, H. Chen, D.A. Rey, F.W. Wise, C.A. Batt, Near-infrared fluorescence imaging with water-soluble lead salt quantum dots, J. Phys. Chem. B 111 (2007) 5726-5730.
28. [28]
  [28] P. Nair, O. Gomezdaza, M. Nair, Metal sulphide thin film photography with lead sulphide thin films, Adv. Mater. Opt. Electron. 1 (1992) 139-145.
29. [29]
  [29] S. Gü nes, K.P. Fritz, H. Neugebauer, et al., Hybrid solar cells using PbS nanoparticles, Sol. Energy Mater. Sol. Cells 91 (2007) 420-423.
30. [30]
  [30] M. Nam, J. Park, S.W. Kim, K. Lee, Broadband-absorbing hybrid solar cells with efficiency greater than 3% based on a bulk heterojunction of PbS quantum dots and a low-bandgap polymer, J. Mater. Chem. A 2 (2014) 3978-3985.
31. [31]
  [31] H. Su, Y. Xie, P. Gao, Y. Xiong, Y. Qian, Synthesis of MS/TiO₂ (M = Pb, Zn, Cd) nanocomposites through a mild sol-gel process, J. Mater. Chem. 11 (2001) 684- 686.
32. [32]
  [32] Y.R. Ma, L.M. Qi, J.M. Ma, H.M. Cheng, Hierarchical, star-shaped PbS crystals formed by a simple solution route, Cryst. Growth Des. 4 (2004) 351-354.
33. [33]
  [33] B. Ding, M.M. Shi, F. Chen, et al., Shape-controlled syntheses of PbS submicro-/nano-crystals via hydrothermal method, J. Cryst. Growth 311 (2009) 1533- 1538.
34. [34]
  [34] F. Chen, W.M. Qiu, X.Q. Chen, M. Wang, H.Z. Chen, Nonsurfactant synthesis of PbS crystals via electrodeposition and hydrothermal methods: from octahedron to maya-pyramid, CrystEngComm 12 (2010) 1893-1898.
35. [35]
  [35] X.H. Zhu, Z.R. Wei, Y.R. Jin, A.P. Xiang, Growth and characterization of a PbI₂ single crystal used for gamma ray detectors, Cryst. Res. Technol. 42 (2007) 456-459.
36. [36]
  [36] K. Shah, F. Olschner, L. Moy, et al., Lead iodide X-ray detection systems, Nucl. Instrum. Methods Phys. Res. Sect. A: Accel. Spectrom. Detect. Assoc. Equip. 380 (1996) 266-270.
37. [37]
  [37] V.H. Fragal, R. Silva, T.P. Cellet, et al., Hosted formation of PbS crystals on polyethylene modified surface, J. Braz. Chem. Soc. 24 (2013) 336-343.
38. [38]
  [38] H.Y. Li, L.A. Estroff, Calcite growth in hydrogels: assessing the mechanism of polymer-network incorporation into single crystals, Adv. Mater. 21 (2009) 470- 473.
39. [39]
  [39] Y. Wang, A. Suna, W. Mahler, R. Kasowski, PbS in polymers. From molecules to bulk solids, J. Chem. Phys. 87 (1987) 7315.
40. [40]
  [40] A.R. Patel, A.V. Rao, An improved design to grow larger and more perfect single crystals in gels, J. Cryst. Growth. 49 (1980) 589-590.
41. [41]
  [41] D. Bhavsar, K. Saraf, Morphology of PbI₂ crystals grown by gel method, Cryst. Res. Technol. 37 (2002) 51-55.
42. [42]
  [42] K. Sangwal, A.R. Patel, Growth features of PbS crystals grown in silica gels, J. Cryst. Growth 23 (1974) 282-288.
43. [43]
  [43] M. Chand, G.C. Trigunayat, Effect of impurities on solid state structure transformations in gel-grown PbI₂ crystals, J. Cryst. Growth 39 (1977) 299-304.
44. [44]
  [44] A. Brif, G. Ankonina, C. Drathen, B. Pokroy, Bio-inspired band gap engineering of zinc oxide by intracrystalline incorporation of amino acids, Adv. Mater. 26 (2014) 477-481.
45. [45]
  [45] M. Sindoro, Y. Feng, S. Xing, et al., Triple-layer (Au@perylene)@polyaniline nanocomposite: unconventional growth of faceted organic nanocrystals on polycrystalline Au, Angew. Chem. Int. Ed. Engl. 50 (2011) 9898-9902.
46. [46]
  [46] Y. Zhao, B.R. Liu, L.J. Pan, G.H. Yu, 3D nanostructured conductive polymer hydrogels for high-performance electrochemical devices, Energy Environ. Sci. 6 (2013) 2856-2870.
47. [47]
  [47] Y. Shi, L.J. Pan, B.R. Liu, et al., Nanostructured conductive polypyrrole hydrogels as high-performance, flexible supercapacitor electrodes, J. Mater. Chem. A 2 (2014) 6086-6091.
48. [48]
  [48] K.Y. Hua, C.M. Deng, C. He, et al., Organic semiconductors-coated polyacrylonitrile (PAN) electrospun nanofibrous mats for highly sensitive chemosensors via evanescent- wave guiding effect, Chin. Chem. Lett. 24 (2013) 643-646.
1. [1]
  Xin Jiang , Han Jiang , Yimin Tang , Huizhu Zhang , Libin Yang , Xiuwen Wang , Bing Zhao . g-C₃N₄/TiO_2-X heterojunction with high-efficiency carrier separation and multiple charge transfer paths for ultrasensitive SERS sensing. Chinese Chemical Letters, 2024, 35(10): 109415-. doi: 10.1016/j.cclet.2023.109415
2. [2]
  Hong-Tao Ji , Yu-Han Lu , Yan-Ting Liu , Yu-Lin Huang , Jiang-Feng Tian , Feng Liu , Yan-Yan Zeng , Hai-Yan Yang , Yong-Hong Zhang , Wei-Min He . Nd@C₃N₄-photoredox/chlorine dual catalyzed synthesis and evaluation of antitumor activities of 4-alkylated sulfonyl ketimines. Chinese Chemical Letters, 2025, 36(2): 110568-. doi: 10.1016/j.cclet.2024.110568
3. [3]
  Min Chen , Boyu Peng , Xuyun Guo , Ye Zhu , Hanying Li . Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors. Chinese Chemical Letters, 2024, 35(4): 109051-. doi: 10.1016/j.cclet.2023.109051
4. [4]
  Meng Lin , Hanrui Chen , Congcong Xu . Preparation and Study of Photo-Enhanced Electrocatalytic Oxygen Evolution Performance of ZIF-67/Copper(I) Oxide Composite: A Recommended Comprehensive Physical Chemistry Experiment. University Chemistry, 2024, 39(4): 163-168. doi: 10.3866/PKU.DXHX202308117
5. [5]
  Xin He , Feng Liu , Tao Tu . Double redox-mediated intrinsic semiconductor photocatalysis: Practical semi-heterogeneous synthesis. Chinese Chemical Letters, 2025, 36(3): 110621-. doi: 10.1016/j.cclet.2024.110621
6. [6]
  Jaeyong Ahn , Zhenping Li , Zhiwei Wang , Ke Gao , Huagui Zhuo , Wanuk Choi , Gang Chang , Xiaobo Shang , Joon Hak Oh . Surface doping effect on the optoelectronic performance of 2D organic crystals based on cyano-substituted perylene diimides. Chinese Chemical Letters, 2024, 35(9): 109777-. doi: 10.1016/j.cclet.2024.109777
7. [7]
  Ziyi Liu , Feifei Guo , Tingting Cao , Youxuan Sun , Xutang Tao , Zeliang Gao . High thermal conductivity in Ga2TeO6 crystals: Synergistic effects of rigid polyhedral frameworks and stereochemically inert cations. Chinese Journal of Structural Chemistry, 2025, 44(4): 100544-100544. doi: 10.1016/j.cjsc.2025.100544
8. [8]
  Xinyu Guo , Chang Li , Wenjun Deng , Yi Zhou , Yan Chen , Yushuang Xu , Rui Li . Phase engineering and heteroatom incorporation enable defect-rich MoS₂ for long life aqueous iron-ion batteries. Chinese Chemical Letters, 2025, 36(3): 109715-. doi: 10.1016/j.cclet.2024.109715
9. [9]
  Muhammad Humayun , Mohamed Bououdina , Abbas Khan , Sajjad Ali , Chundong Wang . Designing single atom catalysts for exceptional electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100193-100193. doi: 10.1016/j.cjsc.2023.100193
10. [10]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
11. [11]
  Qian-Qian Tang , Li-Fang Feng , Zhi-Peng Li , Shi-Hao Wu , Long-Shuai Zhang , Qing Sun , Mei-Feng Wu , Jian-Ping Zou . Single-atom sites regulation by the second-shell doping for efficient electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(9): 109454-. doi: 10.1016/j.cclet.2023.109454
12. [12]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
13. [13]
  Jing Wang , Zhongliao Wang , Jinfeng Zhang , Kai Dai . Single-layer crystalline triazine-based organic framework photocatalysts with different linking groups for H2O2 production. Chinese Journal of Structural Chemistry, 2023, 42(12): 100202-100202. doi: 10.1016/j.cjsc.2023.100202
14. [14]
  Mengjun Sun , Zhi Wang , Jvhui Jiang , Xiaobing Wang , Chuang Yu . Gelation mechanisms of gel polymer electrolytes for zinc-based batteries. Chinese Chemical Letters, 2024, 35(5): 109393-. doi: 10.1016/j.cclet.2023.109393
15. [15]
  Yiwen Xu , Chaozheng He , Chenxu Zhao , Ling Fu . Single-atom Ti doping on S-vacancy two-dimensional CrS₂ as a catalyst for ammonia synthesis: A DFT study. Chinese Chemical Letters, 2025, 36(4): 109797-. doi: 10.1016/j.cclet.2024.109797
16. [16]
  Kunyao Peng , Xianbin Wang , Xingbin Yan . Converting LiNO₃ additive to single nitrogenous component Li₂N₂O₂ SEI layer on Li metal anode in carbonate-based electrolyte. Chinese Chemical Letters, 2024, 35(9): 109274-. doi: 10.1016/j.cclet.2023.109274
17. [17]
  Xingyan Liu , Chaogang Jia , Guangmei Jiang , Chenghua Zhang , Mingzuo Chen , Xiaofei Zhao , Xiaocheng Zhang , Min Fu , Siqi Li , Jie Wu , Yiming Jia , Youzhou He . Single-atom Pd anchored in the porphyrin-center of ultrathin 2D-MOFs as the active center to enhance photocatalytic hydrogen-evolution and NO-removal. Chinese Chemical Letters, 2024, 35(9): 109455-. doi: 10.1016/j.cclet.2023.109455
18. [18]
  Xiujuan Wang , Yijie Wang , Luyun Cui , Wenqiang Gao , Xiao Li , Hong Liu , Weijia Zhou , Jingang Wang . Coordination-based synthesis of Fe single-atom anchored nitrogen-doped carbon nanofibrous membrane for CO₂ electroreduction with nearly 100% CO selectivity. Chinese Chemical Letters, 2024, 35(12): 110031-. doi: 10.1016/j.cclet.2024.110031
19. [19]
  Xin Dong , Jing Liang , Zhijin Xu , Huajie Wu , Lei Wang , Shihai You , Junhua Luo , Lina Li . Exploring centimeter-sized crystals of bismuth-iodide perovskite toward highly sensitive X-ray detection. Chinese Chemical Letters, 2024, 35(6): 108708-. doi: 10.1016/j.cclet.2023.108708
20. [20]
  Jiajing Wu , Ru-Ling Tang , Sheng-Ping Guo . Three types of promising functional building units for designing metal halide nonlinear optical crystals. Chinese Journal of Structural Chemistry, 2024, 43(6): 100291-100291. doi: 10.1016/j.cjsc.2024.100291

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(663)
HTML views(10)

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

Gel-incorporated PbS and PbI2 single-crystals

Metrics

通讯作者: 陈斌, bchen63@163.com

Gel-incorporated PbS and PbI₂ single-crystals