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Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films

Athimotlu Raju Rajamani, Sathiskumar Jothi Orcid Logo, Murugaiah Dhinesh Kumar, Srikaanth Srinivasan, Manoj Kumar Singh, Gonzalo Otero Irurueta, Devaraj Ramasamy, Madhav Datta, Murali Rangarajan

The Journal of Physical Chemistry C

Swansea University Author: Sathiskumar Jothi Orcid Logo

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DOI (Published version): 10.1021/acs.jpcc.6b06924

Abstract

This study presents a systematic examination of the effects of bath additives and deposition conditions on the rates of electrodeposition of bismuth, obtained morphologies, and the ability of the bismuth films to detect trace concentrations of lead. Novel morphologies of bismuth are reported for the...

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Published in: The Journal of Physical Chemistry C
ISSN: 1932-7455
Published: 2016
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URI: https://cronfa.swan.ac.uk/Record/cronfa29895
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The bath comprises bismuth nitrate, nitric acid, and a set of additives, viz., citric acid (complexant), polyvinyl alcohol (surface inhibitor), and betaine (grain refiner). Rotating disk electrode voltammetry and cyclic voltammetry have been used to determine the mechanism and rates of bismuth electrodeposition. Scanning electron microscopy is used to study deposit morphologies, while X-ray diffraction and X-ray photoelectron spectroscopy have been used to examine crystallinity and composition of the deposited thin films. Even in the presence of additives, it is seen that bismuth deposition is diffusion-controlled process with progressive nucleation-growth of crystallites, and the reduction is a single-step, three-electron-transfer, quasi-reversible reaction. The films deposited from the bath without additives comprise micron-sized, hexagonal rods with controlled aspect ratios (1.83 to 2.05). Baths containing citric acid produce films with flower-like structures and cracked grains, but with poor adhesion to copper substrate. Introducing polyvinyl alcohol significantly slows down bismuth deposition, increases the number of nuclei, produces cauliflower-like crystallites, and promotes adhesion to copper. Betaine smoothens these crystallites while retaining good adhesion. Pulsing the deposition current promotes growth of existing nuclei. In the absence of additives, fused flat disk-type spindles are seen. In the presence of additives, pulsed deposition results in sea-urchin-like morphologies. Adhesion of bismuth onto copper impacts the ability of the film to detect trace concentration of Pb2+ ions in aqueous solutions using anodic stripping voltammetry. 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spelling 2018-01-30T10:00:17.7798426 v2 29895 2016-09-12 Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films 6cd28300413d3e63178f0bf7e2130569 0000-0001-7328-1112 Sathiskumar Jothi Sathiskumar Jothi true false 2016-09-12 EEN This study presents a systematic examination of the effects of bath additives and deposition conditions on the rates of electrodeposition of bismuth, obtained morphologies, and the ability of the bismuth films to detect trace concentrations of lead. Novel morphologies of bismuth are reported for the first time. The bath comprises bismuth nitrate, nitric acid, and a set of additives, viz., citric acid (complexant), polyvinyl alcohol (surface inhibitor), and betaine (grain refiner). Rotating disk electrode voltammetry and cyclic voltammetry have been used to determine the mechanism and rates of bismuth electrodeposition. Scanning electron microscopy is used to study deposit morphologies, while X-ray diffraction and X-ray photoelectron spectroscopy have been used to examine crystallinity and composition of the deposited thin films. Even in the presence of additives, it is seen that bismuth deposition is diffusion-controlled process with progressive nucleation-growth of crystallites, and the reduction is a single-step, three-electron-transfer, quasi-reversible reaction. The films deposited from the bath without additives comprise micron-sized, hexagonal rods with controlled aspect ratios (1.83 to 2.05). Baths containing citric acid produce films with flower-like structures and cracked grains, but with poor adhesion to copper substrate. Introducing polyvinyl alcohol significantly slows down bismuth deposition, increases the number of nuclei, produces cauliflower-like crystallites, and promotes adhesion to copper. Betaine smoothens these crystallites while retaining good adhesion. Pulsing the deposition current promotes growth of existing nuclei. In the absence of additives, fused flat disk-type spindles are seen. In the presence of additives, pulsed deposition results in sea-urchin-like morphologies. Adhesion of bismuth onto copper impacts the ability of the film to detect trace concentration of Pb2+ ions in aqueous solutions using anodic stripping voltammetry. The films obtained from baths with additives through direct current plating show the best sensor response for 50 ppb Pb2+. Journal Article The Journal of Physical Chemistry C 1932-7455 31 12 2016 2016-12-31 10.1021/acs.jpcc.6b06924 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2018-01-30T10:00:17.7798426 2016-09-12T09:42:09.4482628 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised Athimotlu Raju Rajamani 1 Sathiskumar Jothi 0000-0001-7328-1112 2 Murugaiah Dhinesh Kumar 3 Srikaanth Srinivasan 4 Manoj Kumar Singh 5 Gonzalo Otero Irurueta 6 Devaraj Ramasamy 7 Madhav Datta 8 Murali Rangarajan 9 0029895-12092016094429.pdf rajamani2016(2).pdf 2016-09-12T09:44:29.8830000 Output 5012438 application/pdf Accepted Manuscript true 2017-09-08T00:00:00.0000000 Supporting information false 0029895-12092016094359.pdf rajamani2016.pdf 2016-09-12T09:43:59.8830000 Output 10404868 application/pdf Accepted Manuscript true 2017-09-08T00:00:00.0000000 false
title Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films
spellingShingle Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films
Sathiskumar Jothi
title_short Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films
title_full Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films
title_fullStr Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films
title_full_unstemmed Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films
title_sort Effects of Additives on Kinetics, Morphologies and Lead-Sensing Property of Electrodeposited Bismuth Films
author_id_str_mv 6cd28300413d3e63178f0bf7e2130569
author_id_fullname_str_mv 6cd28300413d3e63178f0bf7e2130569_***_Sathiskumar Jothi
author Sathiskumar Jothi
author2 Athimotlu Raju Rajamani
Sathiskumar Jothi
Murugaiah Dhinesh Kumar
Srikaanth Srinivasan
Manoj Kumar Singh
Gonzalo Otero Irurueta
Devaraj Ramasamy
Madhav Datta
Murali Rangarajan
format Journal article
container_title The Journal of Physical Chemistry C
publishDate 2016
institution Swansea University
issn 1932-7455
doi_str_mv 10.1021/acs.jpcc.6b06924
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Uncategorised{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Uncategorised
document_store_str 1
active_str 0
description This study presents a systematic examination of the effects of bath additives and deposition conditions on the rates of electrodeposition of bismuth, obtained morphologies, and the ability of the bismuth films to detect trace concentrations of lead. Novel morphologies of bismuth are reported for the first time. The bath comprises bismuth nitrate, nitric acid, and a set of additives, viz., citric acid (complexant), polyvinyl alcohol (surface inhibitor), and betaine (grain refiner). Rotating disk electrode voltammetry and cyclic voltammetry have been used to determine the mechanism and rates of bismuth electrodeposition. Scanning electron microscopy is used to study deposit morphologies, while X-ray diffraction and X-ray photoelectron spectroscopy have been used to examine crystallinity and composition of the deposited thin films. Even in the presence of additives, it is seen that bismuth deposition is diffusion-controlled process with progressive nucleation-growth of crystallites, and the reduction is a single-step, three-electron-transfer, quasi-reversible reaction. The films deposited from the bath without additives comprise micron-sized, hexagonal rods with controlled aspect ratios (1.83 to 2.05). Baths containing citric acid produce films with flower-like structures and cracked grains, but with poor adhesion to copper substrate. Introducing polyvinyl alcohol significantly slows down bismuth deposition, increases the number of nuclei, produces cauliflower-like crystallites, and promotes adhesion to copper. Betaine smoothens these crystallites while retaining good adhesion. Pulsing the deposition current promotes growth of existing nuclei. In the absence of additives, fused flat disk-type spindles are seen. In the presence of additives, pulsed deposition results in sea-urchin-like morphologies. Adhesion of bismuth onto copper impacts the ability of the film to detect trace concentration of Pb2+ ions in aqueous solutions using anodic stripping voltammetry. The films obtained from baths with additives through direct current plating show the best sensor response for 50 ppb Pb2+.
published_date 2016-12-31T03:36:27Z
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score 11.01306

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