Engineering topics

Davey, Adrian K.

Publications and source records attributed to Davey, Adrian K..

4 records

DOE OSTI2022

Enhanced ZIF-8-enabled colorimetric CO 2 sensing through dye-precursor synthesis

The accumulation of carbon dioxide (CO 2 ) within enclosed spaces, along with volatile organic compounds, under certain humidity, temperature, and ventilation conditions is associated with detrimental human health symptoms such as fatigue. Color-based chemical sensing is a promising approach to detect CO 2 levels relevant to indoor air quality through producing fast, quantifiable output visible to the naked eye. In a prior work, a colorimetric gas sensor was fabricated through synthesizing the metal-organic framework, ZIF-8, as the adsorbent, followed by post-synthetic mixing with a dye, phenol red (PSP), and primary amine, ethylenediamine (ED). While this sensor (termed PSP-ED/ZIF-8) maintained its structural integrity in atmospheric conditions and exhibited an increasing fuchsia-to-yellow color change with increasing CO 2 levels in dry environment, the colorimetric response greatly suffered in the presence of humid CO 2 . Here in this work, a significantly improved colorimetric CO 2 sensor (referred to as ED/PSP:ZIF-8) is accomplished through directly incorporating phenol red in the ZIF-8 metal and linker precursor solutions and then blending with ethylenediamine. MATLAB-generated color distributions and in-situ ultraviolet-visible (UV-Vis) spectroscopic studies quantitatively demonstrate an enhanced colorimetric gas response of ED/PSP:ZIF-8 compared to that of PSP-ED/ZIF-8 across an important range of CO 2 for indoor air quality monitoring (500 – 3500 ppm) and across a range of humidity. The new sensor also exhibits high selectivity to CO 2 compared to select volatile organic compounds, such as acetone and ethanol, which contribute to human health symptoms experienced indoors. The enhanced performance is attributed to the proposed incorporation of phenol red within ZIF-8, while maintaining the chemical stability of the MOF.

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DOE OSTI2022

Synthesis and characterization of UiO-66-NH 2 incorporated graphene aerogel composites and their utilization for absorption of organic liquids

This work details the synthesis, materials characterization and absorption capacity of graphene aerogel (GA) loaded with UiO-66-NH 2 metal organic framework (MOF). Throughout the study, a series of density-tunable MOF/GA composites were synthesized by adjusting the MOF/graphene oxide (GO) mass ratio of the precursors before hydrothermal reduction and subsequent critical point drying to achieve MOF-x%/GA composites, with x, ranging from 0 to 100, denoting the weight percent ratio of MOF to GO in the starting solution. Scanning electron microscopy (SEM) images and Barrett-Joyner-Halenda (BJH) pore size calculations supported that MOF loading enlarged the macroporous (>50 nm) structure of the GA framework but had no influence on the mesoporous (2–50 nm) structure of GA. The degree of MOF loading first decreased and then increased the density of resulting composites, exhibiting a minimum for the 10–30% samples. Such behavior with respect to MOF loading has not been reported previously. MOF-x%/GA samples were further investigated for absorption capacity using various organic liquids. MOF-30%/GA proved to be the best absorbent sample for all solvents tested, achieving the highest capacity for chloroform at 147.0 ± 10.0 mg/mg. The behavior is attributed to the structural changes induced by the MOF incorporation as well as the interactions between the organic molecules and the MOF.

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DOE OSTI2022

In-situ synthesized N-doped ZnO for enhanced CO 2 sensing: Experiments and DFT calculations

Chemiresistive CO 2 sensing is attractive due to low cost and ease of chip-level integration. Our previous studies (Yong Xia, 2021) showed the well-developed ZnO material fabricated by in-situ annealing exhibited good CO 2 sensing performance. Here, we have expanded on those studies, including CO 2 cyclic tests under both dry air and N 2 background whereby a much higher response to CO 2 in N 2 background was observed. In this study, detailed density functional theory calculations were conducted to understand the behavior. The results indicated nitrogen doping is mainly responsible for the observed response. In the presence of pre-adsorbed O 2 , N-doped ZnO can no longer interact with CO 2 , which agrees well with the observation of higher response in N 2 background. Furthermore, density of states analysis showed N sp 2 hybridized orbital and N 2p orbital of the N dopant mixed with sp 2 hybridized orbital of C atom and 2p orbitals of C/O atoms in CO 2 to form σ and π bonds, respectively. However, they mixed with O 2s/2p orbitals of O atom in O 2 when pre-adsorbed O 2 was present, hindering CO 2 interaction with N-doped ZnO, and resulting in limited response in air. The illustrated mechanism does not only further the understanding of metal oxide-based CO 2 sensing, but also guide the design of new functional materials for CO 2 sensing or capture.

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DOE OSTI2021

Amine-functionalized metal-organic framework ZIF-8 toward colorimetric CO 2 sensing in indoor air environment

Carbon dioxide (CO 2 ) has been shown to contribute to human health consequences indoors, such as shortness of breath, nasal and optic irritation, dizziness, and nausea. Here in this work, we explore the potential of metal–organic frameworks (MOFs) as highly-porous, crystalline sorbents for sensitive colorimetric CO 2 detection. In particular, the zeolitic imidazolate framework (ZIF-8) is chosen as the sorptive material due to its chemical stability and tunable CO 2 affinity. The colorimetric gas sensor is developed in methanol with three components: (i) MOF ZIF-8 as a high surface area adsorbent; (ii) ethylenediamine (ED) as the CO 2 -affinitive basic function; and (iii) phenolsulfonpthalein (PSP) as the pH indicator. Colorimetric assays and ratiometric analysis confirm a colorimetric response to variable CO 2 concentrations of relevance to indoor air quality. The color response is attributed to a zwitterion mechanism whereby ED reacts with CO 2 to form a zwitterionic intermediate. This intermediate is then deprotonated by the pH indicator, shifting the pH and inducing a color change. Given its simple fabrication, rapid and obvious response, and stability in ambient environment, the ZIF-8-based colorimetric sensor provides a promising route for an improved indoor air quality monitoring.

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