Inhibited combustion of graphene paper by in situ phosphorus doping and its application for fire early-warning sensor
Graphical abstract
Introduction
Fire accidents not only exacerbate safety problems about human life and health, but also lead to adverse effects on atmosphere and ecological balance. Fire accidents affect people's normal life, social and economic developments, and lead to irreparable loss of physical and mental pain. Therefore, development of effective fire prevention methods is a major global challenge. The current fire prevention and mitigation methods include flame retardant, firefighting and fire detection or alarm technologies [[1], [2], [3], [4], [5], [6], [7], [8], [9], [10]].
The early fire-warning plays an important role in active prevention and controlling of fire. To prevent and mitigate the damage caused by fire, many studies about fire monitoring have been carried out based on infrared and smoke detectors. The use of fire detection sensors plays an important role in reducing fire risk of buildings. In general, smoke or infrared detector has been widely used in indoor, by detecting the smoke or light generated from the combustion of combustible materials, usually requiring a long response time of more than 100 s, especially for many cooking scenes [11]. Smoke is generally generated after ignition, and when the concentration of smoke reaches the threshold value of the detectors, they will be triggered for alarm. However, in such situation, fire may develop into full development stage, which is the greatest fire risk scenario. Although conventional fire-warning sensors have been implemented in some fields, these methods have some limitations, such as slow fire response, poor resistance to severe conditions and the limitation of application scenario. Therefore, it is particularly important to develop highly sensitive fire-alarm devices, which will provide timely and reliable fire-alarm signals. In consequence, there is an urgent need for the development of novel fire alarm which can realize fire detection and early warning [12].
Graphene-based materials with excellent chemical and physical properties have attracted increasing attention in catalytic [13], energy conversion and flame-retardant areas [[14], [15], [16]]. Commonly, graphene oxide (GO) is produced by oxidative treatment of graphite via Hummers method [17]. As a derivative or precursor of graphene, GO still retains a graphene-like layered structure. GO consists of oxidized graphene sheets and their basal surfaces are modified mostly with epoxide and hydroxyl groups, and the edges are decorated with carbonyl and carboxyl groups [[18], [19], [20], [21]].
Electrical insulation of GO is explained by the fact that the conjugating electron structure of graphene is destroyed by these oxygen functional groups during chemical oxidation. In the condition of high temperature or flame, most of functional groups on GO can be removed, repairing the conductive network to obtain excellent electrical conductivity [22,23]. This inherent property of GO has provided enormous interest for its possible application in fire-warning field. Great advances have been made in several researches based on electrical resistance transition of GO [24], which is changed from insulation to electrical conduction under fire or high temperature. Dr. Tang from Hangzhou Normal University prepared GO wide-ribbon-coated sponges to reliably detect the potential fire hazard of combustible materials by using the characteristic of temperature-induced electrical resistance transition of GO [25]. Wu et al. from South China University of Technology constructed multiple layers of GO-silicone structures on several substrates and developed as early fire-alarm sensors and fire-retardant coatings. The coating showed distinct temperature-responsive electrical resistance change and exhibited a quick flame-detection response within approximately 3 s when encountering fire [26].
Although the existing researches have made considerable achievements, pure GO paper cannot provide continuous signals due to its poor thermal stability in air [27]. GO paper can be completely burned out under air atmosphere. The work of Huang et al. has improved fire resistance of GO paper through silane-assisted assembling route [28]. Although this modified GO paper can provide an early fire-alarm signal, its preparation process is time-consuming. Therefore, there is an urgent need for developing a simple and low cost fabrication method for advanced GO-based fire response sensors.
Although graphene has excellent performances, its limitation of poor thermal oxidative stability is incontestable, due to the presence of residual oxygen functional groups and defects [29]. Our previous work found that phosphorus doping can improve thermal oxidative stability of graphene. The boron/phosphorus doping retards the oxidation of reduced graphene oxide (RGO) by forming more stable bond configuration. The doped boron/phosphorus atoms restrain carbon gasification and reduce the reactivity of active sites [30]. Inspired from the work, we proposed in-situ phosphorus doping strategy for enhancing thermal stability of graphene. GO paper containing phosphoric acid (PA) was in-situ reduced and doped by phosphorus atoms under fire, and then high electrical conductivity of graphene is repaired and its combustion reaction under air atmosphere is retarded simultaneously.
In this work, PA-modified GO paper (GO-PA) was fabricated by a simple and environmentally friendly water evaporation-assisted self-assembly method. The preparation method is facile without using any organic solvent. We propose a fire-sensor design, which is based on flame-triggered electrical resistance conversion characteristic of GO. The fire alarm circuit consists of GO-PA paper, lamp, wire and low-voltage power. The GO-PA paper exhibits extraordinary rapid flame detection response (within 0.5 s). The GO-PA papers are promising for development of advanced early fire-alarm sensors that can provide quick and continuous signals.
Section snippets
Materials
Graphite powder (granularity ≤30 μm, CP) was provided from Sinopharm Chemical Reagent Co., Ltd. PA solution (≥85 wt% aqueous solution, AR) was obtained from Shanghai Aladdin Biochemical Technology Co., Ltd. All chemicals were used directly without further purification.
Preparation of GO and GO-PA Papers
Graphite powder was oxidized into GO according to Hummers’ method as reported in our previous study [31]. The preparation of GO-PA paper was conducted from its aqueous dispersion by using a simple water evaporation-induced
Characterization of GO and GO-PA Samples
Due to the optimal fire-alarm performance of GO-PA-4 (which will show in the following section), this sample is chosen for the structure and composition characterizations.
The intact GO paper can be peeled from dish after the evaporation of water (Fig. 1a). GO paper can be folded, demonstrating an excellent mechanical flexibility. After introducing PA, the high flexibility of GO paper is not destroyed (Fig. 1d). The microstructures of the prepared papers are observed by SEM images in Fig. 1. It
Conclusions
In this work, GO-PA papers were prepared by a facile, low-cost and easily manipulated evaporation self-assembly approach. The prepared GO-PA papers with different loading of PA exhibit flexible characteristic and stacking microstructure. The hydrogen bonding interactions between GO and PA is confirmed by FTIR spectra. The oxidative decomposition reaction of GO is retarded by the incorporated PA. The addition of PA can improve flame tolerance and duration time of GO strip under fire attacking,
CRediT authorship contribution statement
Gongqing Chen: Investigation, Software, Writing - original draft. Bihe Yuan: Supervision, Writing - review & editing. Yong Wang: Writing - review & editing. Sheng Shang: Methodology, Validation. Xianfeng Chen: Writing - review & editing. Hongji Tao: Data curation. Yuanyuan Zhan: Data curation.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
The authors acknowledge research grant from the National Natural Science Foundation of China (51703175) and the Fundamental Research Funds for the Central Universities (WUT:205261005; WUT:205261007).
Gongqing Chen is now pursuing her MS degree in School of Safety Science and Emergency Management, Wuhan University of Technology China. Her study focuses the design of fire sensors.
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Gongqing Chen is now pursuing her MS degree in School of Safety Science and Emergency Management, Wuhan University of Technology China. Her study focuses the design of fire sensors.
Bihe Yuan received a BS degree in Polymer Material and Engineering from Anhui University in 2011. In 2016, he received a PhD degree in Safety Science and Engineering from State Key Laboratory of Fire Science, University of Science and Technology of China (mentored by Prof. Yuan Hu) and a PhD degree in Architecture and Civil Engineering from City University of Hong Kong (mentored by Prof. Kim Meow Liew). He is currently an associate professor in School of Safety Science and Emergency Management at Wuhan University of Technology. His current research focuses on flame retardant, polymer nanocomposites and fire safety. He has published 90 papers in the peer-reviewed international journals including more than 30 papers as the first and corresponding author.
Yong Wang is now pursuing his MS degree in School of Safety Science and Emergency Management, Wuhan University of Technology China. His research interests include fire safety materials and sensors.
Sheng Shang is now pursuing his MS degree in School of Safety Science and Emergency Management, Wuhan University of Technology China. His research interest includes flame-retardant materials.
Xianfeng Chen is a Professor in Wuhan University of Technology. His research interests include energetic materials and fire safety. About 40 SCI-index articles in the peer-reviewed international journals including two ESI highly cited papers have been published.
Hongji Tao is now pursuing her MS degree in School of Safety Science and Emergency Management, Wuhan University of Technology China. Her study focuses the design of EMI shielding materials.
Yuanyuan Zhan is now pursuing his MS degree in School of Safety Science and Emergency Management, Wuhan University of Technology China. His research interest includes flame-retardant materials.