luận án tiến sĩ nghiên cứu chế tạo vật liệu lai giữa polypyrol và nio cấu trúc nano cho nhạy khí NH3

BỘ GIÁO DỤC VÀ ĐÀO TẠO VIỆN HÀN LÂM KHOA HỌC VÀ CÔNG NGHỆ VIỆT NAM HỌC VIỆN KHOA HỌC VÀ CÔNG NGHỆ - H O À N G T H Ị H I Ế N NGHIÊN CỨU CHẾ TẠO VẬT LIỆU LAI GIỮA POLYPYROL VÀ NiO CẤU TRÚC NANO CHO NHẠY KHÍ NH3 LUẬN ÁN TIẾN SĨ KHOA HỌC VẬT LIỆU Hà Nội, 202 BỘ GIÁO DỤC VÀ ĐÀO TẠO VIỆN HÀN LÂM KHOA HỌC VÀ CÔNG NGHỆ VIỆT NAM HỌC VIỆN KHOA HỌC VÀ CÔNG NGHỆ H O À N G T H Ị H I Ế N NGHIÊN CỨU CHẾ TẠO VẬT LIỆU LAI GIỮA POLYPYROL VÀ NiO CẤU TRÚC NANO C H O N H Ạ Y rần Trung KHÍ NH3 TS Hồ Trƣờng Giang Chuyên ngành: Vật liệu điện tử Mã số: 9440123 LUẬN ÁN TIẾN SĨ KHOA HỌC VẬT LIỆU NGƢỜI HƢỚN G DẪN KHOA HỌC G S T S T LỜI CAM ĐOAN Tôi xin cam đoan công trình nghiên cứu riêng tơi dƣới hƣớng dẫn TS Hồ Trƣờng Giang GS.TS Trần Trung Các số liệu, kết nghiên cứu trung thực chƣa đƣợc công bố tác giả khác cơng trình Tác giả luận án Hồng Thị Hiến LỜI CẢM ƠN Với lịng biết ơn kính trọng sâu sắc, tơi xin gửi lời cảm ơn chân thành tới Thầy, TS Hồ Trƣờng Giang GS.TS Trần Trung, ngƣời Thầy tâm huyết, yêu nghề giao đề tài tận tình hƣớng dẫn tơi, động viên, khích lệ hết lịng giúp đỡ để tơi hồn thành cơng trình nghiên cứu Tôi xin đƣợc gửi lời cảm ơn sâu sắc tới anh, chị, em làm việc Phịng Cảm biến thiết bị đo khí, Viện Khoa học vật liệu, giúp đỡ, hỗ trợ tơi nhiệt tình tạo điều kiện tốt thời gian thực luận án Đồng thời, xin gửi lời cảm ơn tới Lãnh đạo, thầy cô Viện Khoa học vật liệu Học viện Khoa học Cơng nghệ giúp đỡ đóng góp chun mơn q báu Tôi xin gửi lời cảm ơn tới Lãnh đạo, Thầy, Cô đồng nghiệp Bộ môn Vật lý – Khoa Khoa học bản, Trƣờng Đại học Sƣ phạm – Kỹ thuật Hƣng Yên tạo tất điều kiện thuận lợi để tơi tập trung cho việc thực luận án Tôi xin trân trọng cảm ơn PGS.TS Ngạc An Bang, NCS Sái Công Doanh, Trƣờng Đại học Khoa học Tự nhiên, Đại học Quốc gia Hà Nội giúp đỡ nhiệt tình thời gian tơi thực luận án Tôi xin cảm ơn giúp đỡ mặt tài từ nguồn kinh phí đào tạo nghiên cứu sinh nƣớc Bộ Giáo dục Đào tạo (Đề án 911) Đề tài cấp Quốc gia thuộc Chƣơng trình nghiên cứu ứng dụng phát triển công nghệ lƣợng (mã số đề tài KC05.13/16-20) Tôi xin đƣợc dành lời cảm ơn sâu nặng đến gia đình tơi: bố, mẹ, chồng u thƣơng, cảm thơng chia sẻ để tơi tập trung học tập nghiên cứu suốt năm tháng thực luận án Tôi xin chân thành cảm ơn ngƣời thân bạn bè ln động viên khích lệ tơi Nghiên cứu sinh Hoàng Thị Hiến MỤC LỤC MỤC LỤC .i DANH MỤC BẢNG BIỂU ix DANH MỤC KÝ TỰ VIẾT TẮT x MỞ ĐẦU CHƢƠNG 1: TỔNG QUAN 1.1 Polymer dẫn 1.1.1 Khái niệm đời CPs 1.1.2 Một số loại polymer dẫn .7 1.1.3 Cơ chế hình thành polymer .8 1.1.4 Cơ chế dẫn điện CPs polymer dẫn lai hóa vô 10 1.1.5 Ứng dụng vật liệu polymer dẫn polymer lai hóa vơ 15 1.1.6 Phƣơng pháp tổng hợp PPy 15 1.2 Cảm biến khí sở polymer dẫn 18 1.2.1 Giới thiệu cảm biến khí 19 1.2.2 Cảm biến khí NH3 sở polymer dẫn 23 1.2.3 Cảm biến sử dụng polymer dẫn cho khí oxy hóa/khử khác 27 1.2.4 Cảm biến độ ẩm sở polymer dẫn 31 1.2.5 Cơ chế nhạy khí 32 1.3 Kỹ thuật đo sử dụng luận án 37 1.3.1 Hệ khảo sát đặc trƣng nhạy khí 37 1.3.2 Tạo môi trƣờng độ ẩm khác cho khảo sát 39 Kết luận Chƣơng 41 CHƢƠNG 2: TỔNG HỢP VÀ NGHIÊN CỨU CÁC CẤU TRÚC HÌNH THÁI CỦA VẬT LIỆU POLYMER DẪN (PPY, PANI) ẢNH HƢỞNG ĐẾN ĐẶC TRƢNG NHẠY KHÍ NH3 42 i 2.1 Tổng hợp đặc trƣng nhạy khí NH3 cấu trúc hình thái PANi từ phƣơng pháp điện hóa CV 45 2.1.1 Màng PANi tổng hợp phƣơng pháp điện hóa 45 2.1.2 Cấu trúc hình thái học tính chất màng PANi 47 2.1.3 Đặc trƣng nhạy khí NH3 cấu trúc hình thái học PANi 52 2.2 Tổng hợp đặc trƣng nhạy khí NH3 cấu trúc hình thái PPy 54 2.2.1 PPy tổng hợp phƣơng pháp trùng hợp pha 54 2.2.2 Cấu trúc hình thái học tính chất màng PPy 57 2.2.3 Đặc trƣng nhạy khí NH3 cấu trúc hình thái học PPy 64 2.2.4 Thảo luận chế nhạy khí cấu trúc PPy 73 Kết luận Chƣơng 75 CHƢƠNG 3: TỔNG HỢP VÀ NGHIÊN CỨU ĐẶC TRƢNG NHẠY KHÍ NH CỦA VẬT LIỆU LAI NiO/PPy 76 3.1 Tổng hợp màng lai hóa NiO/PPy 77 3.1.1 Chế tạo màng NiO đế Al2O3 78 3.1.2 Chế tạo màng lai hóa màng hạt nano NiO với PPy .79 3.2 Tính chất màng lai hóa NiO/PPy 81 3.2.1 Cấu trúc hình thái 81 3.2.3 Phổ EDX 85 3.2.3 Phổ FTIR 85 3.2.4 Phổ tán xạ Raman 88 3.3 Tính chất nhạy khí màng lai hóa NiO/PPy 90 Kết luận chƣơng .101 KẾT LUẬN CHUNG 102 NHỮNG ĐÓNG GÓP MỚI CỦA LUẬN ÁN .103 DANH MỤC CÁC CƠNG TRÌNH ĐÃ CƠNG BỐ CỦA LUẬN ÁN 104 ii DANH MỤC CÁC CÔNG TRÌNH ĐÃ CƠNG BỐ KHÁC 105 TÀI LIỆU THAM KHẢO 106 iii DANH MỤC HÌNH VẼ Hình 1.1 Ba nhà khoa học Alan J Heeger, Alan MacDiarmid Hideki Shirakawa nhận giải Nobel năm 2000 vật liệu polyme dẫn Hình 1.2 Minh họa cấu trúc phân tử số polyme dẫn điển hình Hình 1.3 Các giai đoạn hình thành PPy từ trùng hợp điện hóa Hình 1.4 Các giai đoạn hình thành PPy từ trùng hợp hóa học sử dụng chất oxy hóa FeCl3 Hình 1.5 Vị trí thang đo độ dẫn điện CPs (PEDOT, PPy, PANi) so sánh với thang kim loại, bán dẫn chất cách điện 11 Hình 1.6 Cấu trúc điện tử cấu trúc hóa học PTh với pha tạp (a) loại p (b) loại n 13 Hình 1.7 (A) Cấu trúc hóa học từ khơng pha tạp tới pha tạp loại p cao PPy; (B) Cấu trúc vùng lƣợng với mức pha tạp khác PPy, (a) không pha tạp, (b) polaron, (c) bipolaron, (d) trạng thái pha tạp đầy đủ .13 Hình 1.8 Sơ đồ khả ứng dụng sở vật liệu CPs 15 Hình 1.9 Minh họa thành phần bình điện hóa cho tổng hợp CPs .16 Hình 1.10 Ảnh SEM dây nano PPy chế tạo phƣơng pháp điện hóa sử dụng khuôn AAO 17 Hình 1.11 Ảnh TEM ống nano PPy đƣợc tổng hợp từ dung dịch chứa FeCl3 MO với thời gian 40 phút 18 Hình 1.12 Mơ hình cấu trúc cảm biến khí độ dẫn/điện trở, (a-c) dạng khối, (df) dạng phẳng; (g-h) cấu trúc xếp lớp nhạy khí điện cực 20 Hình 1.13 Ảnh FE-SEM ống nano PPy đa tƣờng (MPPy NTs): (a) nốt sần nano, (b) dây nano; (c) đáp ứng theo theo thời gian MPPy NTs tiếp xúc với NH3 (10 ppb đến 100 ppm) ethanol (1 ppm đến 10 000 ppm) 23 Hình 1.14 Ảnh TEM (a) đám hạt nano Pd, (b) màng tổ hợp nano PPy/Pd; (c, d) lần lƣợt điện trở đáp ứng độ đáp ứng theo nồng độ khí NH3 từ 50-2000 ppm (1) PPy, (2) PPy/Pd 25 Hình 1.15 (a) Ảnh SEM mẫu CPA dạng cấu trúc lõi/vỏ (CeO2@PANi); (b) đƣờng đáp ứng với nồng độ khí NH3 50, 75 100 ppm tƣơng ứng với tỉ lệ khối lƣợng CeO2 PANi lần lƣợt 0.5, 2, 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CHẾ TẠO VẬT LIỆU LAI GIỮA POLYPYROL VÀ NiO CẤU TRÚC NANO CHO NHẠY KHÍ NH3 LUẬN ÁN TIẾN SĨ KHOA HỌC VẬT LIỆU Hà Nội, 202 BỘ GIÁO DỤC VÀ ĐÀO TẠO VIỆN HÀN LÂM KHOA HỌC VÀ CÔNG... thức cho đơn vị nghiên cứu nƣớc Trên sở này, luận án chọn đề tài với tên ? ?Nghiên cứu chế tạo vật liệu lai polypyrol NiO cấu trúc nano cho nhạy khí NH3? ?? Trong ý tƣởng kết hợp PPy (nhạy tốt với khí. .. với phƣơng pháp chế tạo vật liệu, luận án nghiên cứu cấu trúc nano PPy nhƣ lai hóa PPy với hạt nano NiO để từ minh chứng tồn rõ ràng cấu trúc lai hóa vơ – hữu Mục tiêu luận án - Đánh giá đƣợc ảnh