Graphdiyne nanosheets as a sensing medium for formaldehyde and formic acid – A first-principles outlook

Journal Pre-proofs Graphdiyne nanosheets as a sensing medium for formaldehyde and formic acid – a first-principles outlook R. Bhuvaneswari, J. Princy Maria, V. Nagarajan, R. Chandiramouli PII: DOI: Reference:

S2210-271X(20)30051-7 https://doi.org/10.1016/j.comptc.2020.112751 COMPTC 112751

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Computational & Theoretical Chemistry

Received Date: Revised Date: Accepted Date:

19 December 2019 13 February 2020 18 February 2020

Please cite this article as: R. Bhuvaneswari, J. Princy Maria, V. Nagarajan, R. Chandiramouli, Graphdiyne nanosheets as a sensing medium for formaldehyde and formic acid – a first-principles outlook, Computational & Theoretical Chemistry (2020), doi: https://doi.org/10.1016/j.comptc.2020.112751

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Graphdiyne nanosheets as a sensing medium for formaldehyde and formic acid – a first-principles outlook

R. Bhuvaneswari, J. Princy Maria, V. Nagarajan, R. Chandiramouli* School of Electrical & Electronics Engineering SASTRA Deemed University, Tirumalaisamudram, Thanjavur -613 401, India

*Corresponding Author: Prof. R. Chandiramouli, School of Electrical & Electronics Engineering, SASTRA Deemed University Tel: +919489566466 E-mail: [email protected]

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Abstract Formaldehyde and formic acid (in its vapor form) are considered as target vapors in the current study, and the ability of graphdiyne nanosheet to detect target vapors is scrutinized. First and foremost, the stable conduct of the intended prime material, graphdiyne nanosheet is ascertained with the help of cohesive formation energy. Furthermore, the electronic characteristics like band structure, the projected density of states spectrum and electron density are investigated for the solitary and target vapor adsorbed graphdiyne nanosheet. Finally, the adsorption characteristics of the target vapor on the chief component namely the Bader charge transfer, adsorption energy and average energy gap variation are assessed for all the cases. The investigation, as a whole, suggests the deployment of graphdiyne nanosheet as a chief component in detecting formaldehyde and formic acid vapors. Keywords: Formaldehyde; Formic acid; Graphdiyne; Nanosheet; Adsorption

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1. Introduction The domain of sensors took a huge forward step upon the discovery of renewed and novel two-dimensional (2D) nanostructures (especially those based on group IVA and group VA elements) [1-4]. The inherent and fascinating electronic, optical, and mechanical properties of the 2D nanostructures made it possible for those materials to detect the on hand toxic gas/ vapor molecules in the surroundings [5]. Among the pool of already available 2D nanomaterials, graphdiyne (a non-natural carbon allotrope) entices an extensive group of scientific explorers owing to the structural linearity maintained by the carbon-carbon triple bonds that connect the adjacent benzene rings of graphdiyne [6, 7]. Such a stable allotrope was originally prognosticated by Haley et al. [8] in the year 1997. Later, diverse methods were adopted for easy fabrication of this fascinating nanomaterial on different substrates [9] which is found to possess attracting attributes like supreme electrical conductivity (2.516 x 10-4 S m-1) [9], good chemical and geometrical stability, acceptable mobility (2 x 105 cm2/Vs) [10] and peculiar electronic features for both armchair and zigzag graphdiyne nanotubes. Graphdiyne, which is a 2D one-atom-thick material is ascertained to have its application in a broad scope of fields like nanoelectronics [11], spintronics [12], photocatalysis [13], transistors [14] and accumulators [15]. Moreover, this handily synthesizable, intensely bonded carbon networks i.e., graphdiyne is reported to smoothly detect the existence of CO, H2, CH4 [16], amino acid molecules [17], dimethylamine, trimethylamine [18], NH3 [19], etc., encouraged us to further carry out our research on this unique, appealing nanomaterial. Recently, Xiaojun Li group [20-22] widely studied graphdiyne as a promising material for many potential applications including single atomic catalysts and sensing material. The two target vapors employed in the present study are formic acid and formaldehyde. Formic acid (also known as methanoic acid with a molecular formula HCOOH) is a fuming liquid with a sour taste. It is a potent reducing agent with a pungent, piercing smell. Since the carboxyl 3

group is attached to a hydrogen atom, it can act as both acid and aldehyde (which prevails as a common feature between the two target vapors in the study). Moreover, formic acid is employed as bleaching agents, adhesives, paint additives (industrial uses), insecticides, agricultural chemicals, organic synthetic reagent (agricultural uses) and in paper, cosmetics and rubber products (consumer uses). Upon decomposition, the clear liquid releases spiteful fumes like carbon monoxide. Besides, OSHA (Occupational Safety and health administration) has established the TWA (time-weighted average) for 1-8 hours as 5 ppm (9mg/cu m) and NIOSH (National Institute for Occupation and Safety Health) has also specified 10 hours TWA as 5 ppm [23], despite the utility of formic acid in both industry and agriculture. The ill-effects rendered by formic acid include methanol poisoning, lung cancer, metabolic acidosis, irritable bowel syndrome, ocular injury, rheumatoid arthritis, histotoxic hypoxia, etc. Hence, the IDLH (Immediate danger level exposure) is set to be 30 ppm for formic acid [23]. Formaldehyde with the empirical formula (HCHO) is an achromatic flammable vapor with a peculiar, pungent, and annoying odor. Even though it is naturally found in little quantities in our bodies, the other common sources for formaldehyde are cigarette smoke, smoke from fires (factories) and automobile exhaust. The beneficial uses of formaldehyde are as disinfectants, fertilizers, cosmetics, mouthwashes, preservatives and antiseptics. However, the cancer-causing ability of formaldehyde made OSHA and NIOSH fix the recommended exposure limit as 0.75 ppm for 8 hours TWA and 0.016 ppm for 10 hours TWA, respectively [24]. Besides, formaldehyde prevails as an amidase inhibitor narrowing its target organs to bone marrow, platelet, adipose tissue, fibroblasts, etc. We have studied the interaction properties of sorafenib, regorafenib, imuran, pentasa, hyoscyamine drugs, NH3, dimethylamine and trimethylamine vapors on graphdiyne nanosheets and nanotubes [18, 19, 25, 26]. The state-of-the-art reveals the various allotropes of carbon and its fascinating 4

applications by the researchers. Franco Cataldo et al. [27] studied dinitrogen tetraoxide adsorption on activated carbon fabrics. Recently, many researchers have realized that the carbon-based material namely graphene oxide, buckled penta-graphene and carboxylicfunctionalized graphene, shows good sensing response towards various gas and vapor molecules [28-30]. A.R. Karami [31] studied the surface assimilation of acrolein on graphyne nanotubes. Juan Ren et al. [32] explored hydrogen storage using cobalt decorated graphyne sheets. We studied the interaction properties of explosive vapors such as pentaerythritol tetranitrate, triacetone triperoxide, and octogen on γ-graphyne nanosheets [33]. Now it is time to portrait the fresh focus of the current work, the interaction attributes of formic acid and formaldehyde on graphdiyne nanosheet are studied and reported. 2. Scheming details The intended chief component, graphdiyne nanosheet is initially tested for its firmness with the help of cohesive formation energy using the ATK-VNL package [34, 35]. In order to assess the ability of the graphdiyne nanosheet in detecting the target vapors formic acid and formaldehyde, the electronic attributes like projected density of states spectrum (PDOS), electron density & band structure and surface assimilating features of the target vapor on the chief component namely, the Bader charge transfer, average energy gap variation, and adsorption energy are estimated with the assistance of density functional theory (DFT) method. In particular, Becke86 (B86) and the widely utilized Lee-Yang-Parr (LYP) exchange-correlation functional are employed together with the generalized gradient approximation (GGA) method to investigate the aforementioned properties [36, 37]. Moreover, van-der-Waals dispersion correction is applied to distinguish the interlayer interaction and to compute the target vapor adsorption. Also, the energy cut off is converged to 550 eV where the chief configuration is well substantiated. Furthermore, HellmannFeynman forces are sustained to 0.01 eV/Å by employing the conjugate gradient (CG) 5

algorithm and double zeta polarization (DZP) method. Besides, the Brillouin zones are sampled at the Monkhorst-Pack grid of 15 x 15 x 1 k-points so that atom-level investigation is made [38]. 3. Outcomes and decipherment 3.1.

Structural properties of graphdiyne nanosheet along with electronic

characteristics upon adsorption of formic acid and formaldehyde Graphdiyne, one of the allotropes of group IVA carbon element with unique diacetylenic linkages is employed as a prime component in the present study, which is portrayed in Fig 1. The lattice constant and in-plane atomic bond distance between carbon atoms in graphdiyne has been discussed in our previous reports [19]. Fig. 1 Optimized structure of isolated (3 x 3) super cell of the graphdiyne nanosheet.

The stable conduct is first guaranteed with the assistance of the cohesive formation energy [39] whose equation contains the energy of isolated graphdiyne nanosheet E(GDN), the absolute aggregate of the carbon atoms available in the GDN nanosheet (x) and energy of individual carbon atom E(C). The equation is offered below for the reader’s clarity 6

𝐸𝐶𝑜ℎ =

()

1 [ 𝐸(𝐺𝐷𝑁) - 𝑥𝐸(𝑐)] 𝑥

In accordance with the equation offered above, the value of cohesive formation energy is computed to be -7.495 eV/atom. The large negative magnitude of the cohesive formation energy assures the supreme stable demeanor of the graphdiyne nanosheet [40]. Now, we are turning our focus on the electronic characteristics of the isolated graphdiyne nanosheet. First, the band structure, which offers us a lane to estimate the energy band gap and the projected density of states (PDOS) spectrum [41-45]. Besides, PDOS ensures the estimated value that is reckoned for isolated graphdiyne nanosheet and is sketched in Fig. 2. From the energy band structure, the energy band gap value is figured out to be 0.433 eV (B86LYP), which is shown in Fig. 2. Moreover, the value can be ensured from the PDOS spectrum. The ciphered band gap measure in the current work is validated with previous reports (0.46 eV) [46]. Fig. 2 PDOS and band maps of isolated graphdiyne nanosheet including Brillouin zone.

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Besides, the reported articles suggest that using HSE06 hybrid functional gives more accuracy and nearer to experimental result [47]. Nevertheless, the computational cost is relatively high for HSE06 functional rather than other functional. In the present work, we have utilized B86LYP functional, which is also an optimum choice for studying adsorption studies widely followed by researchers. In addition, the contour in the PDOS spectrum of solitary graphdiyne nanosheet indicates that the p-orbital bestows more rather than the other orbitals to the total density of states (TDOS) spectrum. This is owing to the electronic configuration of C atom. Further, Fig. 3 illustrates the electron density of the solitary graphdiyne nanosheet. The presence of an electron at a specific location at a particular moment can be ascertained from the electron density [48], which is portrayed along with a color gradient. These three estimated parameters of the isolated graphdiyne nanosheet support us in exploring the ability of the prime component (GDN-NS) in sensing the target vapors, formaldehyde, and formic acid.

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Fig. 3 Electron density of isolated graphdiyne nanosheet.

Now, the two target vapors formaldehyde and formic acid are allowed to adsorb on the chief component, graphdiyne nanosheet at three different positions (ring, top and bridge site). The corresponding illustration depicts the adsorption of the two target vapors on three different configurations are supplied in Fig. 4 a – f. Also, designations are made for each adsorbed cases for better understanding to the readers. Besides, configuration 1, 2 and 3 depict formaldehyde adsorption on GDN-NS at the ring, top and bridge site. Likewise, configuration 4, 5 and 6 show formic acid adsorption on GDN-NS at the ring, top and bridge site, respectively. We examined all other promising adsorption sites of target vapors on GDN-NS. About the distance among the GDN-NS and target molecule and binding energy, we ranked out the preferential adsorption (global minima) sites, which are estimated based on previously reported work [49, 50], as shown in Fig. S1 (Supplementary Information). Furthermore, the other interaction sites are neglected from the discussion.

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Fig. 4 (a) Formaldehyde adsorbed on the ring site of graphdiyne nanosheet – configuration 1.

Fig. 4 (b) Formaldehyde adsorbed on the top site of graphdiyne nanosheet – configuration 2.

Fig. 4 (c) Formaldehyde adsorbed on the bridge site of graphdiyne nanosheet – configuration 3.

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Fig. 4 (d) Formic acid adsorbed on the ring site of graphdiyne nanosheet – configuration 4.

Fig. 4 (e) Formic acid adsorbed on top site of graphdiyne nanosheet – configuration 5.

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Fig. 4 (f) Formic acid adsorbed on the bridge site of graphdiyne nanosheet – configuration 6.

The adsorption sites mentioned in the report are global minima positions i.e., they have low binding energy with respect to distance. We traced the global minima positions as illustrated by Ralph H Scheicher's work [49, 50]. The electronic characteristics for the target vapors adsorbed on GDN-NS are computed and explored to confirm the ability of GDN-NS as a base substrate for the detection of formaldehyde and formic acid. Fig. 5 a-f represents the projected density of states (PDOS) spectrum and band structure for the configurations 1-6 (i.e., formaldehyde and formic acid adsorption at the ring, top and bridge sites). The reckoned energy band gap values for configuration 1, 2 and 3 (formaldehyde adsorption) are 0 eV, 0.327 eV and 0.402 eV. It can be evidently perceived that for the ring site (configuration 1), the energy band gap is observed to be 0 eV (semiconductor to metallic transition), which indicates that the current conduction happens without any hindrance.

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Fig. 5 (a) PDOS spectrum and band maps – configuration 1.

Fig. 5 (b) PDOS spectrum and band maps – configuration 2.

Fig. 5 (c) PDOS spectrum and band maps – configuration 3.

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Fig. 5 (d) PDOS spectrum and band maps – configuration 4.

Fig. 5 (e) PDOS spectrum and band maps – configuration 5.

Fig. 5 (f) PDOS spectrum and band maps – configuration 6.

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The current flowing through the nanosheet due to the adsorption of the target vapor can be figured out using the equation provided below [51-54].

(- )

𝜎 = 𝐴[𝑒𝑥𝑝

𝐸𝑔 2𝑘𝑇

]

Herein, A denotes the proportionality constant, Eg signifies the energy band gap, ‘k’ refers to the Boltzmann’s constant and ‘T’ indicates the temperature in Kelvin. The above-mentioned equation furnishes us a relationship between the conductivity and energy band gap, which is useful to us in many ways in estimating the conducting property of GDN-NS. As specified earlier, the semiconducting to metallic transition for configuration 1 influences the flow of current, which can be evidenced from the conductivity equation. Likewise, for configuration 2 and 3, the energy band gap values are found to get decreased to 0.327 eV and 0.402 eV respectively (compared to the pristine energy band gap of 0.433 eV). In accordance with the conductivity equation, this decrease in the energy band gap leads to the enhancement of the current flow through the nanosheet. The computed energy band gap values for configurations 4, 5 and 6 are 0.141 eV, 0.400 eV and 0.433 eV, respectively. Besides, the energy band gap values are found to drastically decrease for configuration 4 (ring site) and it remains the same for the bridge site. The conductivity equation differs on the basis of the values of the band gap. These values are reckoned from the band structure and the correctness of it is validated with the PDOS spectrum of the respective target vapor adsorbed cases. The contour of the PDOS spectrum is noticed to get altered upon the particular target gas interaction at specific sites. But the maximum contribution of p orbital to the TDOS spectrum prevails the same, even upon the target vapor adsorption. This is attributed to the number of carbon atoms available in the GDN-NS. Fig. 6 illustrates the electron density of the target vapor adsorbed graphdiyne nanosheet for different configurations.

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Fig. 6 (a) Electron density – configuration 1.

Fig. 6 (b) Electron density – configuration 2.

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Fig. 6 (c) Electron density – configuration 3.

Fig. 6 (d) Electron density – configuration 4.

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Fig. 6 (e) Electron density – configuration 5.

Fig. 6 (f) Electron density – configuration 6.

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The variation in the measure of electron density upon the surface assimilation of the target vapor is clearly noticed. These three parameters assist us in ensuring the changes that happen at the atomistic level due to the adsorption of the target vapors on GDN-NS. They serve as a seed for us to further continue our exploration on the adsorption attributes of the target vapor on GDN-NS. 3.2.

Formaldehyde and formic acid adsorption characteristics on graphdiyne

nanosheet The structural and electronic characteristics of the isolated and target vapor adsorbed graphdiyne nanosheet paved us a way to validate the capability of the GDN-NS to observe the changes happening in the chief component upon the target vapor adsorption. Now, the adsorption characteristics like Bader charge transfer (Q), adsorption energy (Eads) and average energy gap variation (Ega%) further confirm our implication of employing graphdiyne nanosheet as a chief component in detecting formaldehyde and formic acid. Table 1 displays the estimated parameters of adsorption characteristics. Table 1. Significant factors for investigating the surface assimilation behavior of formaldehyde and formic acid on graphdiyne nanosheet.

Graphdiyne Nanosheet

Bader Adsorption charge energy transfer Ead(eV) Q (e) -

0.433

Average band gap changes Ega (%) -

Configuration 1

-1.502

0.109

0

100

Configuration 2

-0.291

0.117

0.327

24.48

Configuration 3

-0.342

0.155

0.402

07.16

Configuration 4

-0.945

0.239

0.141

67.43

Configuration 5

-0.279

0.197

0.400

07.62

Configuration 6

-0.390

0.198

0.433

0

GDN-NS and configuration

Band gap Eg (eV)

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First, we begin our remarks on the basis of charge transfer. The Bader charge transfer (Q) estimates the charge transfer, which occurs between GDN-NS and the target vapors (formaldehyde and formic acid) [55-60]. In addition, it also determines the orientation of charge transfer. The magnitude of Bader charge transfer for configurations 1-6 is estimated to be 0.109 e, 0.117 e, 0.155 e, 0.239 e, 0.197 e and 0.198 e, respectively. The positive polarity indicates that charge transfer transpires from the considered vapor to the chief component (GDN-NS). Another point to note here is that the target vapors are adsorbed on GDN-NS through the oxygen atom for all the configurations. Even though the electronegativity of oxygen is higher than electronegativity of carbon by nearly a unit magnitude, the presence of the benzene ring (for ring site and top site) and the diacetylinic linkages (for bridge site) makes the charge flow from the target vapor to the chief component. The next parameter to be discussed is adsorption energy which can be calculated from the equation given below [61-64] 𝐸𝑎𝑑𝑠 = [𝐸(𝐺𝐷𝑁 - 𝑡𝑎𝑟𝑔𝑒𝑡 𝑣𝑎𝑝𝑜𝑟) - 𝐸(𝐺𝐷𝑁) - 𝐸(𝑡𝑎𝑟𝑔𝑒𝑡 𝑣𝑎𝑝𝑜𝑟) + 𝐵𝑆𝑆𝐸] The terms utilized in the above equation (from left to right) are the energy of the configuration (target vapor adsorbed GDN-NS), energy of the isolated GDN-NS, energy of the target vapor and basis set superposition energy (BSSE) is computed with the support of counterpoise method so that the aftermaths of overlapping are excluded [65]. The adsorption energy measure is ciphered to be -1.502 eV, -0.291 eV, -0.342 eV, -0.945 eV, -0.279 eV and -0.390 eV for the configurations from 1 to 6. The negative polarity signifies the feasible and smooth adsorption of the target vapor on GDN-NS [66]. In addition, for the configurations from 2 to 6, the physisorption type of adsorption is observed (due to the magnitude of adsorption energy being less than unity) and for configuration 1, mixed type of adsorption is

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noticed. The measure of adsorption energy (for physisorption type) can be confirmed to be within the range expected [67, 68] The average energy gap variation (Ega%) supplies us wisdom on the most useful site for target adsorption to happen [69-71], which is given by the expression,

𝐸𝑎𝑔 =

[

(𝐸𝑔(𝑖𝑠𝑜)~ 𝐸𝑔(𝑐𝑜𝑚𝑝𝑙𝑒𝑥)) 𝐸𝑔(𝑖𝑠𝑜)

]

× 100

were, 𝐸𝑔(𝑖𝑠𝑜) and 𝐸𝑔(𝑐𝑜𝑚𝑝𝑙𝑒𝑥) illustrates the corresponding band gap value of isolated and complex structure of GDN-NS. Even though global minima positions are adopted in the current study for different configurations, the preferable site of target adsorption among the three investigated sites can be figured out through this parameter. The estimated values of energy gap variation for configurations 1, 2 and 3 are 100%, 24.48% and 07.16%, respectively. Among the three sites, ring-site configuration (of formaldehyde adsorption on GDN-NS) is perceived to have a profitable Ega%, which indicates that the sensing response of GDN-NS towards the ring-site adsorption of formaldehyde is at its maximum. This also provides us an added advantage that GDN-NS will never fail in detecting the ring-site adsorption of formaldehyde. Besides, the top-site configuration is at the next position (in terms of Ega). For the configurations 4, 5 and 6, the estimated values are 67.43 %, 07.62 % and 0%. Further, the ring-site configuration (of formic acid on GDN-NS) is found to have a reasonable sensing response. In the worst case, the bridge-site adsorption of formic acid on GDN-NS is not detected. However, the better sensing response obtained by configuration 4 (ring-site) validates the employment of GDN-NS as a chemi-sensor to detect formic acid. Moreover, when configuration 1 and 4 are compared (formaldehyde and formic acid adsorption on the ring-site of GDN-NS), sensing response produced by GDN-NS is observed to be best suited for formaldehyde. This is attributed to the fact that the ionization potential of

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formaldehyde (10.88 eV [72]) is lesser than that of formic acid (11.05 eV [73]). Hence, the three adsorption characteristics affirm our suggestion of utilizing GDN-NS in detecting the target vapors, formaldehyde and formic acid-based on chemiresistive property. 4. Inference and future outlook Graphdiyne nanosheet, one of the allotropes of group IV-A carbon element is used as a base substrate in the study. Besides, GDN-NS stability is established using cohesive formation energy. In order to explore the ability of GDN-NS in detecting the two target vapors formaldehyde and formic acid, the electronic and adsorption characteristics of isolated and target vapor adsorbed GDN-NS are scrutinized with the aid of ATK-VNL software package. The different electronic characteristics like the projected density of states spectrum, band structure, electron density, and various adsorption characteristics like Bader charge transfer, adsorption energy and average energy gap variation are ciphered for all the cases. It is inferred from the above investigation that GDN-NS can be employed as a preferable chief component for chemosensor in detecting formaldehyde and formic acid. Acknowledgement The authors wish to express their sincere thanks to Nano Mission Council (No.SR/NM/NS1011/2017(G)) Department of Science & Technology, India for the financial support.

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Conflict of 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 research article.

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Credit Author Statement All the authors contributed equally to the current work.

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Graphical Abstract

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Research Highlights

 Graphdiyne nanosheets (GDN-NS) are specially designed and its electronic properties are studied  GDN-NS possesses semiconductor properties and used as base material for chemical sensor  Formaldehyde and Formic acid molecules are adsorbed on GDN-NS and nature of adsorption is physisorption  The results suggest that GDN-NS can be used to detect formic acid and formaldehyde vapors

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Declaration of interests

☒ 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.

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