Hóa học sol-gel của các oxit kim loại chuyển tiếp

Progress in Solid State Chemistry - Tập 18 Số 4 - Trang 259-341 - 1988
Thibaud Coradin1, Marc Henry1, Clément Sánchez1
1Laboratoire de Chimie de la Matière Condensée, CNRS (UA 302), UniversitéPierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05, France

Tóm tắt

Quy trình sol-gel mang đến một hướng tiếp cận mới trong việc điều chế thủy tinh và gốm sứ. Xuất phát từ các tiền chất phân tử, một mạng lưới oxit được hình thành thông qua chuỗi phản ứng đa trùng hợp vô cơ. Các phản ứng này diễn ra trong dung dịch, và thuật ngữ “xử lý sol-gel” thường được sử dụng một cách rộng rãi để chỉ các phương pháp tổng hợp oxit vô cơ dựa trên “hóa học ướt”. Quy trình sol-gel mang lại nhiều lợi ích so với phương pháp truyền thống sử dụng “dạng bột”, cụ thể: (1) dễ dàng tạo ra các hệ đa thành phần đồng nhất chỉ bằng cách trộn các dung dịch tiền chất phân tử1,2; (2) nhiệt độ xử lý vật liệu có thể được giảm đáng kể, cho phép tạo ra các loại thủy tinh hoặc gốm sứ có tính chất khác thường3; (3) tính chất lưu biến của các hệ sol và gel cho phép chế tạo sợi, màng hoặc vật liệu composite thông qua các kỹ thuật như kéo sợi4, tráng nhúng5 hoặc thấm ngập6. Những lợi thế này giải thích lý do quá trình sol-gel đã nhận được sự quan tâm đáng kể về mặt khoa học và công nghệ trong thập kỷ vừa qua. Nhiều hội thảo quốc tế hiện nay tập trung vào chủ đề này, chẳng hạn như “Hội thảo Quốc tế về Thủy tinh và Thủy tinh-Gốm từ Gel”7-10, “Quá trình xử lý siêu cấu trúc cho gốm sứ, thủy tinh và composite”11-13 cũng như “Nâng cao chất lượng gốm sứ thông qua hóa học”14,15.

Một đặc tính độc đáo của quy trình sol-gel là khả năng tiến hành từ tiền chất phân tử đến sản phẩm cuối cùng, cho phép kiểm soát tốt hơn toàn bộ quá trình và tổng hợp những vật liệu được “thiết kế theo nhu cầu”. Do đó, để có thể làm chủ quy trình sol-gel, cần chú trọng đến mối liên hệ giữa hoạt tính hóa học, sự hình thành gel và hình thái bột. Bài viết này lần lượt xem xét (i) hóa học của các tiền chất phân tử, (ii) các hiện tượng kết tụ trong quá trình chuyển hóa từ sol-gel thành vật liệu, và (iii) các tính chất vật lý cùng ứng dụng của gel oxit kim loại chuyển tiếp.

Hóa học của quá trình sol-gel dựa trên các phản ứng hydroxyl hóa và ngưng tụ của tiền chất phân tử. Các phản ứng này đã được nghiên cứu sâu rộng trong trường hợp silica16. Tuy nhiên, dữ liệu về tiền chất oxit kim loại chuyển tiếp còn hạn chế. Hai lộ trình tổng hợp thường được mô tả trong tài liệu: (1) sử dụng dung dịch nước của muối vô cơ hoặc (2) sử dụng hợp chất hữu cơ kim loại. Phần đầu tiên của bài viết trình bày hóa học trong môi trường nước của các ion kim loại chuyển tiếp. Đề tài này khá phức tạp do sự tồn tại của nhiều loài phân tử khác nhau, phụ thuộc vào trạng thái oxy hóa, pH, và nồng độ. Thêm vào đó, đối với các cation không mang điện tích bốn, có thể hình thành oxit, hydroxit và thậm chí cả oxo-hydroxit.


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Thông tin xuất bản

Progress in Solid State Chemistry

Tập 18 Số 4

259-341

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