Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium

Zeolites are typically synthesized in alkaline or fluoride-containing near-neutral media. Sophisticated organic structure-directing agents have been investigated for such systems with the aim of discovering materials with unprecedented structures and properties for novel technical applications. In c...

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Main Authors: Guangying Fu, Qiaolin Lang, Xiaolong Liu, Haonuan Zhao, Yiqing Sun, Lei Zhao, Ahmed Omran, Peng Lu, Xiaobo Yang, Bing Yu, Valentin Valtchev
Format: Article
Language:English
Published: KeAi Communications Co., Ltd. 2023-12-01
Series:Green Carbon
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Online Access:http://www.sciencedirect.com/science/article/pii/S2950155523000289
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author Guangying Fu
Qiaolin Lang
Xiaolong Liu
Haonuan Zhao
Yiqing Sun
Lei Zhao
Ahmed Omran
Peng Lu
Xiaobo Yang
Bing Yu
Valentin Valtchev
author_facet Guangying Fu
Qiaolin Lang
Xiaolong Liu
Haonuan Zhao
Yiqing Sun
Lei Zhao
Ahmed Omran
Peng Lu
Xiaobo Yang
Bing Yu
Valentin Valtchev
author_sort Guangying Fu
collection DOAJ
description Zeolites are typically synthesized in alkaline or fluoride-containing near-neutral media. Sophisticated organic structure-directing agents have been investigated for such systems with the aim of discovering materials with unprecedented structures and properties for novel technical applications. In contrast, zeolite crystallization in strongly acidic media has yet to be explored. This study demonstrates that a zeolitic silicate phase crystallizes from acidic gels using trimethylamine as an organic additive with the composition 1 SiO2:0.3 TMA:0.3 HCl: 0.15 HF:55 H2O:(0.1–0.4) GeO2. This phase has an interrupted four-connected framework analog to the octahedron/tetrahedron-mixed framework of the mineral family pharmacosiderite. In comparison to the pharmacosiderite-type HK3(Ge7O16)(H2O)4, the four GeO6-octahedra forming the central [HGe4O4O12]-cluster are replaced by four SiO4-tetrahedra in a [Si4O6(OH)2.89]-unit in the new phase. However, the structure is distorted and may contain connectivity and point defects; thus, healing by the occasional incorporation of GeO6-units is necessary. The refined unit cell has a cubic symmetry, space group P-43m (#215), with a = 7.7005(1) Å. Acidic-medium synthesis is a useful way to find new zeolites that move in a fundamentally different direction from sophisticated organic structure-directing agents.
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publisher KeAi Communications Co., Ltd.
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spelling doaj-art-e3f6e7921a9c4cffa7257c4f47a648142025-08-20T03:42:43ZengKeAi Communications Co., Ltd.Green Carbon2950-15552023-12-011218519210.1016/j.greenca.2023.11.003Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic mediumGuangying Fu0Qiaolin Lang1Xiaolong Liu2Haonuan Zhao3Yiqing Sun4Lei Zhao5Ahmed Omran6Peng Lu7Xiaobo Yang8Bing Yu9Valentin Valtchev10The ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, ChinaThe ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, ChinaThe ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, China; College of Chemistry and Chemical Engineering, Qingdao University, 266071 Qingdao, ChinaNormandie University, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, F-14000 Caen, FranceThe ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, China; College of Chemistry and Chemical Engineering, Qingdao University, 266071 Qingdao, ChinaThe ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, ChinaNormandie University, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, F-14000 Caen, FranceThe ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, ChinaThe ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, China; Corresponding authors.College of Chemistry and Chemical Engineering, Qingdao University, 266071 Qingdao, China; Corresponding authors.The ZeoMat Group, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Science, Laoshan District, 266101 Qingdao, China; Normandie University, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, F-14000 Caen, France; Corresponding authors.Zeolites are typically synthesized in alkaline or fluoride-containing near-neutral media. Sophisticated organic structure-directing agents have been investigated for such systems with the aim of discovering materials with unprecedented structures and properties for novel technical applications. In contrast, zeolite crystallization in strongly acidic media has yet to be explored. This study demonstrates that a zeolitic silicate phase crystallizes from acidic gels using trimethylamine as an organic additive with the composition 1 SiO2:0.3 TMA:0.3 HCl: 0.15 HF:55 H2O:(0.1–0.4) GeO2. This phase has an interrupted four-connected framework analog to the octahedron/tetrahedron-mixed framework of the mineral family pharmacosiderite. In comparison to the pharmacosiderite-type HK3(Ge7O16)(H2O)4, the four GeO6-octahedra forming the central [HGe4O4O12]-cluster are replaced by four SiO4-tetrahedra in a [Si4O6(OH)2.89]-unit in the new phase. However, the structure is distorted and may contain connectivity and point defects; thus, healing by the occasional incorporation of GeO6-units is necessary. The refined unit cell has a cubic symmetry, space group P-43m (#215), with a = 7.7005(1) Å. Acidic-medium synthesis is a useful way to find new zeolites that move in a fundamentally different direction from sophisticated organic structure-directing agents.http://www.sciencedirect.com/science/article/pii/S2950155523000289Zeolite synthesis in acidic mediumNew germanosilicate zeolite4-connected analogue of pharmacosideriteStructure analysisStructure-directing agents
spellingShingle Guangying Fu
Qiaolin Lang
Xiaolong Liu
Haonuan Zhao
Yiqing Sun
Lei Zhao
Ahmed Omran
Peng Lu
Xiaobo Yang
Bing Yu
Valentin Valtchev
Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium
Green Carbon
Zeolite synthesis in acidic medium
New germanosilicate zeolite
4-connected analogue of pharmacosiderite
Structure analysis
Structure-directing agents
title Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium
title_full Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium
title_fullStr Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium
title_full_unstemmed Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium
title_short Zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium
title_sort zeolitic germanosilicate analogue to pharmacosiderite crystallized in an acidic medium
topic Zeolite synthesis in acidic medium
New germanosilicate zeolite
4-connected analogue of pharmacosiderite
Structure analysis
Structure-directing agents
url http://www.sciencedirect.com/science/article/pii/S2950155523000289
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