Next Article in Journal
Study of the Performance of Emulsified Asphalt Shotcrete in High-Altitude Permafrost Regions
Next Article in Special Issue
Effect of Humidity on Interfacial Debonding Behavior Between Larger Graphene Sheet and Cement-Based Composites
Previous Article in Journal
Oxidation Resistance of Ir/HfO2 Composite Coating Prepared by Chemical Vapor Deposition: Microstructure and Elemental Migration
Previous Article in Special Issue
Finite Element Analysis Study of Buried Crack Defects in B-Sleeve Fillet Welds
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Coatings
Volume 14
Issue 6
10.3390/coatings14060694
coatings-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

The Effects of Halogen (Cl, Br) Decorating on the Gas Adsorption Behaviors of the Pristine Black Phosphorene: A First-Principles Study

by
Xinjun Tan
1,
Lan Lin
2,
Touwen Fan
2,3,* and
Kaiwang Zhang
1,*
1
School of Physics and Optoelectronics, Xiangtan University, Xiangtan 411105, China
2
Research Institute of Automobile Parts Technology, Hunan Institute of Technology, Hengyang 421002, China
3
School of Science, Hunan Institute of Technology, Hengyang 421002, China
*
Authors to whom correspondence should be addressed.
Coatings 2024, 14(6), 694; https://doi.org/10.3390/coatings14060694
Submission received: 16 March 2024 / Revised: 22 May 2024 / Accepted: 29 May 2024 / Published: 1 June 2024
(This article belongs to the Special Issue Recent Progress in Surface and Interface Properties of Nanostructures)
Browse Figures
Versions Notes

Abstract

:
As a novel two-dimensional (2D) material, black phosphorene (BP) finds wide applications in gas adsorption and detection devices due to its distinctive optical, thermoelectric, and surface properties. However, numerous studies have demonstrated that BP exhibits strong selectivity towards gas adsorption and displays significant affinity towards gas molecules containing the element N, thereby greatly impeding its utilization in gas detection. To partially compensate for this deficiency, this study investigates the impact of halogen atom decoration on the adsorption behavior of BP towards CO2, H2O, and O2 molecules. Furthermore, a comparison is made between the variations in gas adsorption energy with and without decorated halogen atoms. The results showed that the adsorbates of CO2, H2O, and O2 molecules and halogen atoms (Cl, Br) adsorbed at the top (T) site of BP was much stronger than those at the bridge (B) and the hollow (H) sites of the P-P bond of BP, owing to their low adsorption energies. After the t position of BP is modified by the halogen (Cl, Br) atom, the optimal adsorption of CO2 changes from −0.85 eV to −1.70 eV (Cl) and −1.64 eV (Br), and the optimal adsorption of H2O changes from −0.72 eV to −1.48 eV (Cl) and −1.23 eV (Br), respectively. The adsorption properties were significantly enhanced. That is to say, the gas adsorption properties of BP have been largely improved by halogen Cl (Br) atoms decorating.

1. Introduction

In recent years, 2D materials have garnered significant research interest [1,2,3,4,5,6,7] due to their unique structure [8,9], electronic and thermoelectric properties [10,11,12,13], as well as their superior specific surface area. These materials have made breakthroughs in ionic batteries [14,15], catalysts [16,17,18,19,20,21], gas sensors [22,23,24,25,26], and gas trapping. Black phosphorene (BP) is a new 2D material discovered after graphene and is expected to be an important supplement [27,28,29,30]. As a semiconductor layered material [27,29,31,32,33,34,35], its electronic structure has a significant relationship with the number of layers and exhibits excellent electrical transport properties. The weak van der Waals force between the layers [36,37] facilitates easy embedding and diffusion of ions, enabling them to be stripped into single 2D diene phosphate. Different from some other 2D planar structures, phosphorene possesses an armchair-oriented intelligent crumped structure [38], which imparts it with anisotropic physical and chemical properties, with extremely high room temperature carrier mobility, quantum Hall effect, extremely high specific surface area, high Young’s modulus, good optical transmittance, and good electrical and thermal conductivity [32,35,39,40,41]. Compared with other 2D materials such as graphene and MoS2, BP has higher electron mobility [42,43,44], and the leakage current modulation rate is 104~105 times that of graphene, and low-layer BP field-effect transistor (FET) with high mobility at about 1000 cm2V−1s−1 has been reported [43]. The optical and optoelectronic properties of BP exhibit significant advantages [29,39,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67]. The band gap of BP is adjustable [43,68,69,70,71], which can be adjusted by changing the stack number of phosphorene layers [72,73,74], and has obvious anisotropy [75,76,77]. The low-layer BP has been predicted as an ideal direct band gap material at the Γ point, which is a very important property for electron and optical applications [78]. In addition, BP has unique anisotropic photoelectric properties, which has a good application prospect in anisotropic nano-photoelectric devices [79,80,81,82,83]. The heterogeneous composite structure based on BP can improve its inherent performance and further expand its application in the field of energy storage and conversion. For example, BP complexes can provide more reaction sites in electrocatalysis, promote interfacial electron transfer, and eventually stabilize their own structures [78]. It can also improve the conductivity of the battery, inhibit volume expansion, stabilize the electrode and electrolyte interface, and increase the stored energy. Therefore, it is of great significance to study the performance of BP for its wider application.
Koenig et al. [45] measured the electric field effect of thin layers of BP, indicating that BP is suitable for making field-effect transistors. The few-layer BP field effect transistors (FETs) have been reported to exhibit exceptional characteristics, including high carrier mobility, anisotropic transport behavior, remarkable on/off ratios, and elevated operating frequencies [84]. Lv et al. [85] found that sulfur doping in BP can effectively improve its stability. Deng et al. [86] prepared photodiodes by combining P-type BP with N-type single-layer disulfide using van der Waals force. Kulish et al. [87] used first-principles calculations to study the main trends of the electronic structure and mechanical properties of BP as a function of sodium ion concentration. Guo et al. [88] successfully prepared medium-infrared light detectors with BP. Therefore, it has good application prospects in future semiconductor, solar cells, solar fuel production, supercapacitors, energy storage and conversion, sensors, biomedicine, and other fields [89,90,91,92,93,94,95,96,97,98,99,100,101,102,103,104,105,106,107,108,109,110,111,112,113,114,115,116,117,118].
In addition to its unique electrical, optical, and thermoelectric properties, BP is also used for gas adsorption and detection due to its unique surface properties. Other common two-dimensional materials such as single-wall carbon nanotubes (SWCNTS) were reported by Jones AC. Dillon et al. as early as 1997 for hydrogen storage [119]. In 2005, Yildirim et al. further improved the hydrogen storage capacity by modifying metal atoms on CNTS [120]. Based on the large surface ratio and surface characteristics, CNT nano-gas sensors show high detection accuracy in H2, NO2, NH3, water vapor, and other gas sensing. Since 2D material BP also has a large surface–volume ratio, this property can also be relied upon for gas detection applications. Kou et al. studied the adsorption effect of various gas molecules on monolayer BP by theoretical calculation based on Green’s function method and found that black phosphorene has good sensitivity to NO and NO2 [121]. Cai et al. also studied the adsorption of BP by small molecules, and the theoretical results also showed strong adsorption capacity for NO2 [122]. Sibari et al. have employed two atomic potentials, namely optB88-vdW and meta-GGA potentials, to study the adsorption behaviors of NH3, NO, NO2, CO, and CO2 gas molecules on a black phosphorene surface at several coverages [123]. They found from the adsorption energies per molecule that the functionals start to behave differently as the coverage rate increases, and the significant charge transfer between NO and NO2 molecules and black phosphorene suggests its potential integration towards efficient nitrogen-oxide detectors. Li et al. studied the metal modification on BP and obtained the hydrogen storage efficiency of 8.11 wt% [124]. However, many studies have shown that BP has strong selectivity for gas adsorption and can produce strong adsorption for gas molecules containing element N, which greatly inhibits the trial scope of BP in gas detection. The fatal flaw of BP is the lack of stability. When exposed to water and oxygen, the BP sheet oxidizes and degrades in a very short time. This defect greatly limits the research and industrial application of BP.
It has been reported that graphene can form a stable structure after being chlorinated. Nasim et al. studied Cl-modified alkene phosphate and predicted that it could be used as cathode material for N-type chloride ion batteries [125]. In addition, the adsorption of different atoms (such as F, Cl, Br, I) on the surface of phosphorylated alkenes has a significant effect on its structure and electronic properties [126]. For example, it can cause the transition of phosphorene from a direct bandgap semiconductor to an indirect bandgap semiconductor and induce a spin-polarized defect state [127]. Plutnar et al. [128] experimentally reported successful binding of fluorine to BP, indicating a possible pathway for the introduction of other functional groups by fluorine substitution.
To make up the gap of gas detection and improve the stability of BP, the BP surface was modified by halogen. The effects of CO2, H2O, and O2 on adsorption were investigated by comparing the effects of BP and decorative halogen on BP. The calculation shows that the addition of halogen atoms plays an active role in the adsorption of BP and improves the stability of BP to a certain extent. At the same time, the different adsorption positions also affect the adsorption performance of BP.

2. Methods and Models

2.1. Computational Methods

In this paper, based on the first-principles calculation of pseudopotential plane waves in the density functional theory (DFT), the single-layer BP was optimized using Vienna ab initio simulation software package (VASP.5.4.4) [129]. The Kohn–Sham equation was solved by using the total energy method of plane waves to obtain valence electron density and wave function [130]. And the Perdew–Burke–Ernzerhof (PBE) version of the generalized gradient approximation (GGA) was used to describe the exchange correlation function [131,132,133]. The projected enhanced wave (PAW) method is used to describe the electron-ion interaction [133,134,135,136], and the empirical correction of van der Waals force under the Grimme framework (DFT + D2) is carried out. Ionized electron interactions were simulated using ultrasoft pseudopotential [137,138]. To ensure the accuracy of the calculation, the cut-off energy was set as 500 eV, the Gamma centered was set by the Monkhorst–Pack method [139,140], and the K-point grids were set to be 3 × 2 × 3 for all cases. In the process of common gradient optimization, the maximum Hellmann–Feynman force of each atom was less than 0.01 eV/Å [141]. The cell shape and internal atomic coordinates relax completely until the total energy variation resulting from electron relaxation is less than 10−6 eV/atom. Since the periodicity of the boundary is imposed in the transverse direction of the plane, we introduce enough vacuum space of 15 Å in the longitudinal direction to avoid the interaction between adjacent proto sublayers, which can affect the calculation results. The adsorption energy (Eads) of adsorbate on the BP is usually computed by subtracting isolate energies of bare BP and adsorbent from the complex system and can be expressed as follows [142]:
E ads = E BP + adsorbate − E BP − E adsorbate
where E BP + adsorbate , E BP   and   E adsorbate   are the total energies of the adsorbate-monolayer BP system, pristine BP, and adsorbate, respectively. It should be noted that the adsorbate are the CO2, H2O, O2 molecules and halogen atoms.

2.2. BP Model and Gas Adsorption Model

To study the effects of halogen (Cl, Br) decorating on the gas adsorption properties of the pristine BP, the structure of BP monolayer was firstly analyzed. Figure 1a–c show the side, perspective, and vertical views of pristine BP, respectively. The single-layer BP has a fold structure in the direction of the armchair. Although BP is composed of phosphorus atoms, there are two non-equivalent P-P bonds, T12 = T13 = 2.223 Å and T14 = 2.256 Å, and two unequal bond angles, being θ213 = 96.248° and θ214 = θ314 = 103.622°. The calculated lattice constants of pristine BP are also shown in Figure 1c, being a = 4.56 Å and b = 3.41 Å. The obtained results exhibit excellent consistency with the findings from other available data [143,144,145,146,147,148]. The distinctive geometric structure of BP serves as the fundamental cause for its anisotropy.

2.3. The Effects of Halogen Atoms Decorating on the Adsorption Properties of BP Monolayer

The adsorption of gas molecules CO2, O2, and H2O on BP was firstly constructed, as shown in the vertical view of Figure 2. Three adsorption positions should be considered, namely the top (T-sites) of the phosphorene atom, the middle vacancy hollow (H-sites), and the bridge (B-sites) of the P-P bond. At the same time, the red atom M represents the halogen adatoms (F, Cl, Br, I, and At) on the BP; therefore, there are 15 situations in total.
Taking the H-position as an example, Figure 3a–c indicate that CO2 can exist along three directions, Figure 3d,e indicate that O2 can contain two directions, and Figure 3f–j show that H2O presents five model structures, with a total of 30 structural adsorption models. The initial adsorption distance of all the above models is set to be 2.50 Å.
When Eads is negative, it refers to the exothermic reaction between the adsorbates and phosphorene, and the larger the value, the stronger the interaction between the adsorbates and the phosphorene surface [123,125]. When the halogen atoms are combined with phosphorene, they form a stable structure, which also indicates that the halogen atoms will be adsorbed on the surface of phosphorene instead of forming Cl dimers or Cl–clusters [149]. The simulation results show that compared with H- and B-sites, halogens decorated (except F atom) on the BP in the T-site have the smallest adsorption energy, and the adsorption energies of the five decorating atoms of F, Cl, Br, I, and At at the T-site of BP are increased sequentially, being −3.11, −1.22, −0.95, 0.40, and −0.20 eV, respectively. And the optimized distances between halogen atoms and BP are 1.69, 2.24, 2.47, 2.73, and 2.82 Å, respectively, according to the adsorption calculation results of the model in Figure 2. After close analysis, it is rationally expected that since with increasing weight of the halogen the distance between the atom and the surface increases, the stabilization of adsorption due to charge transfer becomes smaller, and the net result is that the adsorption energy becomes less negative. The results are in general agreement with the other theoretical prediction of −3.25, −1.80, −1.40, −1.07 eV for adsorbed energy and 1.68, 2.21, 2.44, 2.70 Å for adsorbed distance, for F, Cl, Br, and I, respectively [127]. The halogen atoms Br and Cl are commonly employed for experimental decoration purposes due to their ready availability and low toxicity [127]. Here, we have selected them for further adsorbing CO2, O2, and H2O gas molecules for the investigation. The original distance between halogen atoms and all gas molecules is also set to be 2.50 Å.

3. Results and Discussion

Table 1 shows the relaxed spacing between BP and adsorbate. It was found that the decorating distance of every halogen atom was maintained equally at the three positions. However, at the same position, the spacing of decorated halogen atoms with the BP increases with the increase in atomic number. In the gas adsorption of CO2, H2O, and O2, the different direction and position will affect the adsorption spacing and change the adsorption behavior of the gas. Compared with B- and H-sites, the adsorption spacing of CO2, H2O, and O2 at T-sites changes the least.
Table 1. Parameter changes before and after adsorption of adsorbate, as well as changes in the distance between BP and the adsorbate. The numbers in the table are arranged in sequence in the direction of gas molecules, as shown in Figure 4.
Table 1. Parameter changes before and after adsorption of adsorbate, as well as changes in the distance between BP and the adsorbate. The numbers in the table are arranged in sequence in the direction of gas molecules, as shown in Figure 4.
AdsorbatesdT (Å)dB (Å)dH (Å)
F1.691.691.69
Cl2.242.242.24
Br2.472.472.47
I2.732.722.72
At2.822.822.82
CO2-13.303.423.24
CO2-23.323.333.39
CO2-33.333.052.94
H2O-13.173.092.86
H2O-23.383.132.90
H2O-33.343.142.90
H2O-43.323.322.91
H2O-53.323.282.91
O2-11.662.752.77
O2-22.612.522.52
Table 2 shows the adsorption energies of adsorbates at the T-, B-, and H-sites of the BP, and the curves of the adsorption energies vs. elements are illustrated in Figure 5. It can be seen from Figure 5a that the adsorption energy of halogen elements on BP shows a strong regularity of increasing with the increase in atomic number, and the variation trend of adsorption energy at the three positions (T, B, H) are consistent. Even the adsorption energy values of B- and H-sites were very similar, with an error of only 0.01 eV. It can be seen from Figure 5 and Table 2 that the adsorption energy of the F atom at the T-site is −3.11 eV, which is slightly larger than the −3.45 eV for both B- and H-sites. Whereas, the adsorption energy of the Cl atom at the T-site on BP, of the order of −1.22 eV, is lower than that of B- and H-sites of the BP, of the order of −1.18 eV, which indicates that the Cl atom prefers decorating on the T-site of the BP.
From Figure 5b–d, it was found that the regularity of each gas adsorbate is not obvious in comparison to the three positions (T, B, H), since there was no relation to the change of atomic number, and there is no strong continuity in the direction selection of gas adsorbates. Therefore, we only discuss the direction and position of each gas molecule in which the adsorption performance is the best. It can be seen from Figure 5b that for the adsorption of CO2 on the BP, the adsorption energy values of −0.85 eV for CO2-1 at the T-sites are the lowest and far smaller than those for B- and H-sites, being −0.44 eV and −0.46 eV, respectively. At the same time, the adsorption energy of CO2-3 at the B-site is the lowest, being −0.61 eV, and is far smaller than that for H- and T-sites, being −0.40 eV and −0.41 eV, respectively. Whereas, the adsorption energies of CO2-2 at three points present a slight difference. From Figure 5c, we can see that the adsorption energy of O2-1 at the T-site of BP was −1.99 eV and was much smaller than other cases. The adsorption energies for O2-1 at the H- and B-sites of BP, and O2-2 at the T-, B-, and H-sites of BP, show little difference, and are all smaller than that for CO2 and H2O molecules. As shown in Figure 5d, the adsorption energies of H2O-2~5 at the H-site are very similar, and the adsorption energy changes only by 0.01 eV. For both T- and B-sites, it is obvious that the adsorption performance of H2O-2 is the best, and the adsorption energies are −0.72 eV and −0.50 eV, respectively.
To clearly illustrate the adsorption energy difference between different configurations at the same site of BP, the data in Figure 5 are redrawn in Figure 6a–c. It is clearly seen from Figure 6a that the adsorption energy of O2-1 at the T-site of BP has the smallest value, while the adsorption energies for other cases are all higher than −1.0 eV. Whereas, the O2-2 configuration at both B- and H-sites of BP possess the same smallest values, also much smaller than the others.
In conclusion, the optimal adsorption for all considered gas molecules, CO2, H2O, and O2, were at the T-site of BP, and the best adsorption configurations of CO2, O2, and H2O are CO2-1, O2-1, and H2O-2, respectively. At the B- and H-sites of BP decorated by halogen atoms, the adsorption model showed that halogen atoms would move to T-sites.
Then, the effects of halogen (Cl, Br) decorating on the gas adsorption behaviors of the pristine BP are investigated based on the first-principles calculations. The halogen atoms Cl and Br are selected for the study. The adsorption energies of gas molecules CO2, H2O, and O2 on the halogen (Cl, Br)-decorated BP have been calculated, and the results are summarized in Table 3 and illustrated in Figure 7. Compared with Table 2, it is found that the optimal adsorption of CO2 changed from −0.85 eV to −1.70 eV (Cl) and −1.64 eV (Br), expanding to 2 and 1.9 times that of the originals, respectively, and the adsorption performance is significantly enhanced. At the same time, the optimal adsorption of H2O changes from −0.72 eV to −1.48 eV (Cl) and −1.23 eV (Br), respectively, and the adsorption energy of O2 changes from −1.99 eV to −2.09 eV (Cl) and −2.00 eV (Br), respectively; although, the adsorption of O2-1 is not greatly improved, the adsorption energy of O2-2 is increased by 3 times, which significantly enhanced its adsorption capacity to a large extent. Furthermore, in the adsorption of Cl-decorating BP, the optimal adsorption energy is increased by 2 times, while the Br atom is slightly lower, except for O2. Obviously, based on BP decorated by the Cl atom, the adsorption effect of gas is better than the Br atom, the adsorption effect is twice that of the original gas adsorption, and the adsorption performance is obviously enhanced.

4. Conclusions

Based on the first-principles calculations, we have studied the adsorption behaviors of the gas molecules of CO2, H2O, and O2 on black phosphorene (BP) with and without halogen atoms decorated. The results show that among the three positions, namely the top (T) site on the P atom, the bridge (B) and the hollow (H) sites of the P-P bond of the original BP, the adsorption performance of all gas molecules and all halogen atoms (except for F atom) at the T-sites were the best. The results of Cl (Br) atomic modification on T-sites of BP show that the adsorption properties of gas after chemical modification are significantly improved compared with the original gas adsorption. The BP decorated by Cl atom can enlarge the adsorption energy of gas by about 2 times, which is better than that modified by the Br atom. Combined with this study, the modification of large-area Cl atoms at the T position in BP is expected to improve the testing range of BP in gas detection to a certain extent.

Author Contributions

Conceptualization, X.T. and T.F.; Methodology, X.T., L.L. and T.F.; Software, X.T., L.L. and T.F.; Validation, X.T. and L.L.; Formal analysis, X.T., L.L. and T.F.; Investigation, L.L. and T.F.; Resources, T.F. and K.Z.; Data curation, X.T., L.L. and T.F.; Writing—original draft, L.L.; Writing—review & editing, X.T. and T.F.; Visualization, X.T. and L.L.; Supervision, T.F. and K.Z.; Project administration, X.T., T.F. and K.Z.; Funding acquisition, X.T. and T.F. All authors have read and agreed to the published version of the manuscript.

Funding

This work is supported by the National Natural Science Foundation of China (52371009), the Scientific Research Project of Hunan Institute of Technology (HQ21016, 21A0564, HP21047), and the PhD innovation project of Xiangtan University (XDCX2019B064).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Liu, Y.; Guo, J.; He, Q.; Wu, H.; Cheng, H.-C.; Ding, M.; Shakir, I.; Gambin, V.; Huang, Y.; Duan, X. Vertical charge transport and negative transconductance in multilayer molybdenum disulfides. Nano Lett. 2017, 17, 5495–5501. [Google Scholar] [CrossRef]
  2. Manzeli, S.; Ovchinnikov, D.; Pasquier, D.; Yazyev, O.V.; Kis, A. 2D transition metal dichalcogenides. Nat. Rev. Mater. 2017, 2, 17033. [Google Scholar] [CrossRef]
  3. Novoselov, K.S.; Jiang, D.; Schedin, F.; Booth, T.; Khotkevich, V.; Morozov, S.; Geim, A.K. Two-dimensional atomic crystals. Proc. Natl. Acad. Sci. USA 2005, 102, 10451–10453. [Google Scholar] [CrossRef]
  4. Novoselov, K.S.; Mishchenko, A.; Carvalho, O.A.; Castro Neto, A. 2D materials and van der Waals heterostructures. Science 2016, 353, aac9439. [Google Scholar] [CrossRef]
  5. Pang, X.; Qin, L.; Xu, B.; Liu, Q.; Yu, Y. Ultralarge contraction directed by light-driven unlocking of prestored strain energy in linear liquid crystal polymer fibers. Adv. Funct. Mater. 2020, 30, 2002451. [Google Scholar] [CrossRef]
  6. Zhang, H. Ultrathin two-dimensional nanomaterials. ACS Nano 2015, 9, 9451–9469. [Google Scholar] [CrossRef]
  7. Zhang, S.; Guo, S.; Chen, Z.; Wang, Y.; Gao, H.; Gómez-Herrero, J.; Ares, P.; Zamora, F.; Zhu, Z.; Zeng, H. Recent progress in 2D group-VA semiconductors: From theory to experiment. Chem. Soc. Rev. 2018, 47, 982–1021. [Google Scholar] [CrossRef]
  8. Persson, I.; Halim, J.; Lind, H.; Hansen, T.W.; Wagner, J.B.; Näslund, L.Å.; Darakchieva, V.; Palisaitis, J.; Rosen, J.; Persson, P.O. 2D transition metal carbides (MXenes) for carbon capture. Adv. Mater. 2019, 31, 1805472. [Google Scholar] [CrossRef]
  9. Wang, B.; Zhou, A.; Liu, F.; Cao, J.; Wang, L.; Hu, Q. Carbon dioxide adsorption of two-dimensional carbide MXenes. J. Adv. Ceram. 2018, 7, 237–245. [Google Scholar] [CrossRef]
  10. Ares, P.; Novoselov, K.S. Recent advances in graphene and other 2D materials. Nano Mater. Sci. 2022, 4, 3–9. [Google Scholar] [CrossRef]
  11. Champagne, A.; Charlier, J.-C. Physical properties of 2D MXenes: From a theoretical perspective. J. Phys. Mater. 2020, 3, 032006. [Google Scholar] [CrossRef]
  12. Liu, Y.; Zhang, S.; He, J.; Wang, Z.M.; Liu, Z. Recent progress in the fabrication, properties, and devices of heterostructures based on 2D materials. Nano-Micro Lett. 2019, 11, 13. [Google Scholar] [CrossRef]
  13. Gupta, A.; Sakthivel, T.; Seal, S. Recent development in 2D materials beyond graphene. Prog. Mater. Sci. 2015, 73, 44–126. [Google Scholar] [CrossRef]
  14. Chang, Y.-M.; Lin, H.-W.; Li, L.-J.; Chen, H.-Y. Two-dimensional materials as anodes for sodium-ion batteries. Mater. Today Adv. 2020, 6, 100054. [Google Scholar] [CrossRef]
  15. Xiao, Y.; Ding, Y.; Cheng, H.; Lu, Z. The potential application of 2D Ti2CT2 (T=C, O and S) monolayer MXenes as anodes for Na-ion batteries: A theoretical study. Comput. Mater. Sci. 2019, 163, 267–277. [Google Scholar] [CrossRef]
  16. Liu, D.; Barbar, A.; Najam, T.; Javed, M.S.; Shen, J.; Tsiakaras, P.; Cai, X. Single noble metal atoms doped 2D materials for catalysis. Appl. Catal. B Environ. 2021, 297, 120389. [Google Scholar] [CrossRef]
  17. Gao, Y.; Zhuo, H.; Cao, Y.; Sun, X.; Zhuang, G.; Deng, S.; Zhong, X.; Wei, Z.; Wang, J. A theoretical study of electrocatalytic ammonia synthesis on single metal atom/MXene. Chin. J. Catal. 2019, 40, 152–159. [Google Scholar] [CrossRef]
  18. Peng, J.; Chen, X.; Ong, W.-J.; Zhao, X.; Li, N. Surface and heterointerface engineering of 2D MXenes and their nanocomposites: Insights into electro-and photocatalysis. Chem 2019, 5, 18–50. [Google Scholar] [CrossRef]
  19. Wang, Y.; Mao, J.; Meng, X.; Yu, L.; Deng, D.; Bao, X. Catalysis with two-dimensional materials confining single atoms: Concept, design, and applications. Chem. Rev. 2018, 119, 1806–1854. [Google Scholar] [CrossRef]
  20. Zhu, J.; Ha, E.; Zhao, G.; Zhou, Y.; Huang, D.; Yue, G.; Hu, L.; Sun, N.; Wang, Y.; Lee, L.Y.S. Recent advance in MXenes: A promising 2D material for catalysis, sensor and chemical adsorption. Coord. Chem. Rev. 2017, 352, 306–327. [Google Scholar] [CrossRef]
  21. Gao, G.; O’Mullane, A.P.; Du, A. 2D MXenes: A new family of promising catalysts for the hydrogen evolution reaction. Acs Catal. 2017, 7, 494–500. [Google Scholar] [CrossRef]
  22. Wang, Y.; Ma, S.; Wang, L.; Jiao, Z. A novel highly selective and sensitive NH3 gas sensor based on monolayer Hf2CO2. Appl. Surf. Sci. 2019, 492, 116–124. [Google Scholar] [CrossRef]
  23. Rajkumar, K.; Kumar, R.R. Gas sensors based on two-dimensional materials and its mechanisms. In Fundamentals and Sensing Applications of 2D Materials; Elsevier: Amsterdam, The Netherlands, 2019; pp. 205–258. [Google Scholar]
  24. Joshi, N.; Hayasaka, T.; Liu, Y.; Liu, H.; Oliveira, O.N.; Lin, L. A review on chemiresistive room temperature gas sensors based on metal oxide nanostructures, graphene and 2D transition metal dichalcogenides. Microchim. Acta 2018, 185, 213. [Google Scholar] [CrossRef]
  25. Tang, X.; Du, A.; Kou, L. Gas sensing and capturing based on two-dimensional layered materials: Overview from theoretical perspective. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2018, 8, e1361. [Google Scholar] [CrossRef]
  26. Varghese, S.S.; Lonkar, S.; Singh, K.; Swaminathan, S.; Abdala, A. Recent advances in graphene based gas sensors. Sens. Actuators B Chem. 2015, 218, 160–183. [Google Scholar] [CrossRef]
  27. Li, L.; Yu, Y.; Ye, G.J.; Ge, Q.; Ou, X.; Wu, H.; Feng, D.; Chen, X.H.; Zhang, Y. Black phosphorus field-effect transistors. Nat. Nanotechnol. 2014, 9, 372–377. [Google Scholar] [CrossRef]
  28. Liu, H.; Neal, A.T.; Zhu, Z.; Tomanek, D.; Ye, P.D. Phosphorene: A new 2D material with high carrier mobility. arXiv 2014, arXiv:1401.4133. [Google Scholar]
  29. Buscema, M.; Groenendijk, D.J.; Blanter, S.I.; Steele, G.A.; Van Der Zant, H.S.; Castellanos-Gomez, A. Fast and broadband photoresponse of few-layer black phosphorus field-effect transistors. Nano Lett. 2014, 14, 3347–3352. [Google Scholar] [CrossRef]
  30. Wang, G.; Pandey, R.; Karna, S.P. Effects of extrinsic point defects in phosphorene: B, C, N, O, and F adatoms. Appl. Phys. Lett. 2015, 106, 173104. [Google Scholar] [CrossRef]
  31. Wan, B.; Zhou, Q.; Zhang, J.; Wang, Y.; Yang, B.; Lv, W.; Zhang, B.; Zeng, Z.; Chen, Q.; Wang, J. Enhanced Stability of Black Phosphorus Field-Effect Transistors via Hydrogen Treatment. Adv. Electron. Mater. 2018, 4, 1700455. [Google Scholar] [CrossRef]
  32. Xia, F.; Wang, H.; Jia, Y. Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics. Nat. Commun. 2014, 5, 4458. [Google Scholar] [CrossRef]
  33. Tran, V.; Soklaski, R.; Liang, Y.; Yang, L. Layer-controlled band gap and anisotropic excitons in few-layer black phosphorus. Phys. Rev. B Condens. Matter 2014, 89, 235319. [Google Scholar] [CrossRef]
  34. Engel, M.; Steiner, M.; Avouris, P. Black phosphorus photodetector for multispectral, high-resolution imaging. Nano Lett. 2014, 14, 6414–6417. [Google Scholar] [CrossRef]
  35. Das, S.; Zhang, W.; Demarteau, M.; Hoffmann, A.; Dubey, M.; Roelofs, A. Tunable transport gap in phosphorene. Nano Lett. 2014, 14, 5733–5739. [Google Scholar] [CrossRef]
  36. Li, Q.; Zhou, Q.; Niu, X.; Zhao, Y.; Chen, Q.; Wang, J. Covalent functionalization of black phosphorus from first-principles. J. Phys. Chem. Lett. 2016, 7, 4540–4546. [Google Scholar] [CrossRef]
  37. Kou, L.; Chen, C.; Smith, S.C. Phosphorene: Fabrication, properties, and applications. J. Phys. Chem. Lett. 2015, 6, 2794–2805. [Google Scholar] [CrossRef]
  38. Rodin, A.; Carvalho, A.; Neto, A.C. Strain-induced gap modification in black phosphorus. Phys. Rev. Lett. 2014, 112, 176801. [Google Scholar] [CrossRef]
  39. Liu, H.; Neal, A.T.; Zhu, Z.; Luo, Z.; Xu, X.; Tománek, D.; Ye, P.D. Phosphorene: An unexplored 2D semiconductor with a high hole mobility. ACS Nano 2014, 8, 4033–4041. [Google Scholar] [CrossRef]
  40. Castellanos-Gomez, A. Black phosphorus: Narrow gap, wide applications. J. Phys. Chem. Lett. 2015, 6, 4280–4291. [Google Scholar] [CrossRef]
  41. Geim, A.K.; Novoselov, K.S. The rise of graphene. Nat. Mater. 2007, 6, 183–191. [Google Scholar] [CrossRef]
  42. Zhang, X.; Zhao, X.; Wu, D.; Jing, Y.; Zhou, Z. MnPSe3 monolayer: A promising 2D visible-light photohydrolytic catalyst with high carrier mobility. Adv. Sci. 2016, 3, 1600062. [Google Scholar] [CrossRef]
  43. Sun, S.; Meng, F.; Wang, H.; Wang, H.; Ni, Y. Novel two-dimensional semiconductor SnP 3: High stability, tunable bandgaps and high carrier mobility explored using first-principles calculations. J. Mater. Chem. A 2018, 6, 11890–11897. [Google Scholar] [CrossRef]
  44. Wang, Y.; Huang, P.; Ye, M.; Quhe, R.; Pan, Y.; Zhang, H.; Zhong, H.; Shi, J.; Lu, J. Many-body effect, carrier mobility, and device performance of hexagonal arsenene and antimonene. Chem. Mater. 2017, 29, 2191–2201. [Google Scholar] [CrossRef]
  45. Koenig, S.P.; Doganov, R.A.; Schmidt, H.; Castro Neto, A.; Özyilmaz, B. Electric field effect in ultrathin black phosphorus. Appl. Phys. Lett. 2014, 104, 103106. [Google Scholar] [CrossRef]
  46. Doganov, R.A.; Koenig, S.P.; Yeo, Y.; Watanabe, K.; Taniguchi, T.; Özyilmaz, B. Transport properties of ultrathin black phosphorus on hexagonal boron nitride. Appl. Phys. Lett. 2015, 106, 083505. [Google Scholar] [CrossRef]
  47. Kamalakar, M.V.; Madhushankar, B.; Dankert, A.; Dash, S.P. Effect of high-k dielectric and ionic liquid gate on nanolayer black-phosphorus field effect transistors. Appl. Phys. Lett. 2015, 107, 113103. [Google Scholar] [CrossRef]
  48. Deng, B.; Tran, V.; Xie, Y.; Jiang, H.; Li, C.; Guo, Q.; Wang, X.; Tian, H.; Koester, S.J.; Wang, H. Efficient electrical control of thin-film black phosphorus bandgap. Nat. Commun. 2017, 8, 14474. [Google Scholar] [CrossRef]
  49. Ahmed, F.; Kim, Y.D.; Yang, Z.; He, P.; Hwang, E.; Yang, H.; Hone, J.; Yoo, W.J. Impact ionization by hot carriers in a black phosphorus field effect transistor. Adv. Mater. Technol. 2018, 9, 3414. [Google Scholar] [CrossRef]
  50. Chen, Y.; Ren, R.; Pu, H.; Chang, J.; Mao, S.; Chen, J. Field-effect transistor biosensors with two-dimensional black phosphorus nanosheets. Biosens. Bioelectron. 2017, 89, 505–510. [Google Scholar] [CrossRef]
  51. Chen, C.; Youngblood, N.; Peng, R.; Yoo, D.; Mohr, D.A.; Johnson, T.W.; Oh, S.-H.; Li, M. Three-dimensional integration of black phosphorus photodetector with silicon photonics and nanoplasmonics. Nano Lett. 2017, 17, 985–991. [Google Scholar] [CrossRef]
  52. Chen, X.; Lu, X.; Deng, B.; Sinai, O.; Shao, Y.; Li, C.; Yuan, S.; Tran, V.; Watanabe, K.; Taniguchi, T. Widely tunable black phosphorus mid-infrared photodetector. Nat. Commun. 2017, 8, 1672. [Google Scholar] [CrossRef]
  53. Ren, X.; Li, Z.; Huang, Z.; Sang, D.; Qiao, H.; Qi, X.; Li, J.; Zhong, J.; Zhang, H. Environmentally robust black phosphorus nanosheets in solution: Application for self-powered photodetector. Adv. Funct. Mater. 2017, 27, 1606834. [Google Scholar] [CrossRef]
  54. Zhang, M.; Wu, Q.; Zhang, F.; Chen, L.; Jin, X.; Hu, Y.; Zheng, Z.; Zhang, H. 2D black phosphorus saturable absorbers for ultrafast photonics. Adv. Opt. Mater. 2019, 7, 1800224. [Google Scholar] [CrossRef]
  55. He, J.; Tao, L.; Zhang, H.; Zhou, B.; Li, J. Emerging 2D materials beyond graphene for ultrashort pulse generation in fiber lasers. Nanoscale 2019, 11, 2577–2593. [Google Scholar] [CrossRef]
  56. Wang, Y.; Zhang, F.; Tang, X.; Chen, X.; Chen, Y.; Huang, W.; Liang, Z.; Wu, L.; Ge, Y.; Song, Y. All-optical phosphorene phase modulator with enhanced stability under ambient conditions. Laser Photonics Rev. 2018, 12, 1800016. [Google Scholar] [CrossRef]
  57. Tang, S.; He, Z.; Liang, G.; Chen, S.; Ge, Y.; Sang, D.K.; Lu, J.; Lu, S.; Wen, Q.; Zhang, H. Pulse duration dependent nonlinear optical response in black phosphorus dispersions. Opt. Commun. 2018, 406, 244–248. [Google Scholar] [CrossRef]
  58. Shi, J.; Li, Z.; Sang, D.K.; Xiang, Y.; Li, J.; Zhang, S.; Zhang, H. THz photonics in two dimensional materials and metamaterials: Properties, devices and prospects. J. Mater. Chem. C 2018, 6, 1291–1306. [Google Scholar] [CrossRef]
  59. Liu, J.; Chen, Y.; Li, Y.; Zhang, H.; Zheng, S.; Xu, S. Switchable dual-wavelength Q-switched fiber laser using multilayer black phosphorus as a saturable absorber. Photonics Res. 2018, 6, 198–203. [Google Scholar] [CrossRef]
  60. Bao, X.; Ou, Q.; Xu, Z.Q.; Zhang, Y.; Bao, Q.; Zhang, H. Band structure engineering in 2D materials for optoelectronic applications. Adv. Mater. Technol. 2018, 3, 1800072. [Google Scholar] [CrossRef]
  61. Zhou, Y.; Zhang, M.; Guo, Z.; Miao, L.; Han, S.-T.; Wang, Z.; Zhang, X.; Zhang, H.; Peng, Z. Recent advances in black phosphorus-based photonics, electronics, sensors and energy devices. Mater. Horiz. 2017, 4, 997–1019. [Google Scholar] [CrossRef]
  62. Xu, Y.; Wang, W.; Ge, Y.; Guo, H.; Zhang, X.; Chen, S.; Deng, Y.; Lu, Z.; Zhang, H. Stabilization of black phosphorous quantum dots in PMMA nanofiber film and broadband nonlinear optics and ultrafast photonics application. Adv. Funct. Mater. 2017, 27, 1702437. [Google Scholar] [CrossRef]
  63. Liu, Y.; Shivananju, B.N.; Wang, Y.; Zhang, Y.; Yu, W.; Xiao, S.; Sun, T.; Ma, W.; Mu, H.; Lin, S. Highly efficient and air-stable infrared photodetector based on 2D layered graphene–black phosphorus heterostructure. ACS Appl. Mater. Interfaces 2017, 9, 36137–36145. [Google Scholar] [CrossRef]
  64. Liu, S.; Li, Z.; Ge, Y.; Wang, H.; Yue, R.; Jiang, X.; Li, J.; Wen, Q.; Zhang, H. Graphene/phosphorene nano-heterojunction: Facile synthesis, nonlinear optics, and ultrafast photonics applications with enhanced performance. Photonics Res. 2017, 5, 662–668. [Google Scholar] [CrossRef]
  65. Jiang, X.-F.; Zeng, Z.; Li, S.; Guo, Z.; Zhang, H.; Huang, F.; Xu, Q.-H. Tunable broadband nonlinear optical properties of black phosphorus quantum dots for femtosecond laser pulses. Materials 2017, 10, 210. [Google Scholar] [CrossRef]
  66. Ge, Y.; Chen, S.; Xu, Y.; He, Z.; Liang, Z.; Chen, Y.; Song, Y.; Fan, D.; Zhang, K.; Zhang, H. Few-layer selenium-doped black phosphorus: Synthesis, nonlinear optical properties and ultrafast photonics applications. J. Mater. Chem. C 2017, 5, 6129–6135. [Google Scholar] [CrossRef]
  67. Du, J.; Zhang, M.; Guo, Z.; Chen, J.; Zhu, X.; Hu, G.; Peng, P.; Zheng, Z.; Zhang, H. Phosphorene quantum dot saturable absorbers for ultrafast fiber lasers. Sci. Rep. 2017, 7, 42357. [Google Scholar] [CrossRef]
  68. Kovalenko, M.V.; Protesescu, L.; Bodnarchuk, M.I. Properties and potential optoelectronic applications of lead halide perovskite nanocrystals. Science 2017, 358, 745–750. [Google Scholar] [CrossRef]
  69. Mortazavi, B.; Rabczuk, T. Anisotropic mechanical properties and strain tuneable band-gap in single-layer SiP, SiAs, GeP and GeAs. Phys. E Low-Dimens. Syst. Nanostruct. 2018, 103, 273–278. [Google Scholar] [CrossRef]
  70. Zhang, S.; Guo, S.; Huang, Y.; Zhu, Z.; Cai, B.; Xie, M.; Zhou, W.; Zeng, H. Two-dimensional SiP: An unexplored direct band-gap semiconductor. 2D Mater. 2016, 4, 015030. [Google Scholar] [CrossRef]
  71. Xie, Z.; Wang, D.; Fan, T.; Xing, C.; Li, Z.; Tao, W.; Liu, L.; Bao, S.; Fan, D.; Zhang, H. Black phosphorus analogue tin sulfide nanosheets: Synthesis and application as near-infrared photothermal agents and drug delivery platforms for cancer therapy. J. Mater. Chem. B 2018, 6, 4747–4755. [Google Scholar] [CrossRef]
  72. Li, L.; Kim, J.; Jin, C.; Ye, G.J.; Qiu, D.Y.; Da Jornada, F.H.; Shi, Z.; Chen, L.; Zhang, Z.; Yang, F. Direct observation of the layer-dependent electronic structure in phosphorene. Nat. Nanotechnol. 2017, 12, 21–25. [Google Scholar] [CrossRef]
  73. Zhang, G.; Huang, S.; Chaves, A.; Song, C.; Özçelik, V.O.; Low, T.; Yan, H. Infrared fingerprints of few-layer black phosphorus. Nat. Commun. 2017, 8, 14071. [Google Scholar] [CrossRef]
  74. Wang, X.; Jones, A.M.; Seyler, K.L.; Tran, V.; Jia, Y.; Zhao, H.; Wang, H.; Yang, L.; Xu, X.; Xia, F. Highly anisotropic and robust excitons in monolayer black phosphorus. Nat. Nanotechnol. 2015, 10, 517–521. [Google Scholar] [CrossRef]
  75. Schuster, R.; Trinckauf, J.; Habenicht, C.; Knupfer, M.; Büchner, B. Anisotropic particle-hole excitations in black phosphorus. Phys. Rev. Lett. 2015, 115, 026404. [Google Scholar] [CrossRef]
  76. Mei, P.; Kim, J.; Kumar, N.A.; Pramanik, M.; Kobayashi, N.; Sugahara, Y.; Yamauchi, Y. Phosphorus-based mesoporous materials for energy storage and conversion. Joule 2018, 2, 2289–2306. [Google Scholar] [CrossRef]
  77. Pang, J.; Bachmatiuk, A.; Yin, Y.; Trzebicka, B.; Zhao, L.; Fu, L.; Mendes, R.G.; Gemming, T.; Liu, Z.; Rummeli, M.H. Applications of phosphorene and black phosphorus in energy conversion and storage devices. Adv. Energy Mater. 2018, 8, 1702093. [Google Scholar] [CrossRef]
  78. Qiao, J.; Kong, X.; Hu, Z.-X.; Yang, F.; Ji, W. High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus. Nat. Commun. 2014, 5, 4475. [Google Scholar] [CrossRef]
  79. Yuan, H.; Liu, X.; Afshinmanesh, F.; Li, W.; Xu, G.; Sun, J.; Lian, B.; Curto, A.G.; Ye, G.; Hikita, Y. Polarization-sensitive broadband photodetector using a black phosphorus vertical P–N junction. Nat. Nanotechnol. 2015, 10, 707–713. [Google Scholar] [CrossRef]
  80. Sherrott, M.C.; Whitney, W.S.; Jariwala, D.; Biswas, S.; Went, C.M.; Wong, J.; Rossman, G.R.; Atwater, H.A. Anisotropic quantum well electro-optics in few-layer black phosphorus. Nano Lett. 2018, 19, 269–276. [Google Scholar] [CrossRef]
  81. Chen, C.; Lu, X.; Deng, B.; Chen, X.; Guo, Q.; Li, C.; Ma, C.; Yuan, S.; Sung, E.; Watanabe, K. Widely tunable mid-infrared light emission in thin-film black phosphorus. Sci. Adv. 2020, 6, eaay6134. [Google Scholar] [CrossRef]
  82. Huang, S.; Lu, Y.; Wang, F.; Lei, Y.; Song, C.; Zhang, J.; Xing, Q.; Wang, C.; Xie, Y.; Mu, L. Layer-dependent pressure effect on the electronic structure of 2D black phosphorus. Phys. Rev. Lett. 2021, 127, 186401. [Google Scholar] [CrossRef]
  83. Wang, J.; Rousseau, A.; Yang, M.; Low, T.; Francoeur, S.; Kéna-Cohen, S. Mid-infrared polarized emission from black phosphorus light-emitting diodes. Nano Lett. 2020, 20, 3651–3655. [Google Scholar] [CrossRef]
  84. Liu, X.; Ang, K.W.; Yu, W.; He, J.; Feng, X.; Liu, Q.; Jiang, H.; Tang, D.; Wen, J.; Lu, Y.; et al. Black Phosphorus Based Field Effect Transistors with Simultaneously Achieved Near Ideal Subthreshold Swing and High Hole Mobility at Room Temperature. Sci. Rep. 2016, 6, 24920. [Google Scholar] [CrossRef]
  85. Lv, W.; Yang, B.; Wang, B.; Wan, W.; Ge, Y.; Yang, R.; Hao, C.; Xiang, J.; Zhang, B.; Zeng, Z. Sulfur-doped black phosphorus field-effect transistors with enhanced stability. ACS Appl. Mater. Interfaces 2018, 10, 9663–9668. [Google Scholar] [CrossRef]
  86. Deng, Y.; Luo, Z.; Conrad, N.J.; Liu, H.; Gong, Y.; Najmaei, S.; Ajayan, P.M.; Lou, J.; Xu, X.; Ye, P.D. Black phosphorus–monolayer MoS2 van der Waals heterojunction P–N diode. ACS Nano 2014, 8, 8292–8299. [Google Scholar] [CrossRef]
  87. Kulish, V.V.; Malyi, O.I.; Persson, C.; Wu, P. Phosphorene as an anode material for Na-ion batteries: A first-principles study. Phys. Chem. Chem. Phys. 2015, 17, 13921–13928. [Google Scholar] [CrossRef]
  88. Guo, Q.; Pospischil, A.; Bhuiyan, M.; Jiang, H.; Tian, H.; Farmer, D.; Deng, B.; Li, C.; Han, S.-J.; Wang, H. Black phosphorus mid-infrared photodetectors with high gain. Nano Lett. 2016, 16, 4648–4655. [Google Scholar] [CrossRef]
  89. Abate, Y.; Akinwande, D.; Gamage, S.; Wang, H.; Snure, M.; Poudel, N.; Cronin, S.B. Recent progress on stability and passivation of black phosphorus. Adv. Mater. 2018, 30, 1704749. [Google Scholar] [CrossRef]
  90. Shriber, P.; Samanta, A.; Nessim, G.D.; Grinberg, I. First-principles investigation of black phosphorus synthesis. J. Mater. Chem. A 2018, 9, 1759–1764. [Google Scholar] [CrossRef]
  91. Luo, M.; Fan, T.; Zhou, Y.; Zhang, H.; Mei, L. 2D black phosphorus–based biomedical applications. Adv. Funct. Mater. 2019, 29, 1808306. [Google Scholar] [CrossRef]
  92. Reina, G.; González-Domínguez, J.M.; Criado, A.; Vázquez, E.; Bianco, A.; Prato, M. Promises, facts and challenges for graphene in biomedical applications. Chem. Soc. Rev. 2017, 46, 4400–4416. [Google Scholar] [CrossRef]
  93. Zhang, B.; Wei, P.; Zhou, Z.; Wei, T. Interactions of graphene with mammalian cells: Molecular mechanisms and biomedical insights. Adv. Drug Deliv. Rev. 2016, 105, 145–162. [Google Scholar] [CrossRef]
  94. Dai, S.; Tymchenko, M.; Xu, Z.-Q.; Tran, T.T.; Yang, Y.; Ma, Q.; Watanabe, K.; Taniguchi, T.; Jarillo-Herrero, P.; Aharonovich, I. Internal nanostructure diagnosis with hyperbolic phonon polaritons in hexagonal boron nitride. Nano Lett. 2018, 18, 5205–5210. [Google Scholar] [CrossRef]
  95. Zhang, A.; Li, A.; Zhao, W.; Liu, J. Recent advances in functional polymer decorated two-dimensional transition-metal dichalcogenides nanomaterials for chemo-photothermal therapy. Chem. Eur. J. 2018, 24, 4215–4227. [Google Scholar] [CrossRef]
  96. Hynek, J.; Zelenka, J.; Rathouský, J.I.; Kubát, P.; Ruml, T.S.; Demel, J.; Lang, K. Designing porphyrinic covalent organic frameworks for the photodynamic inactivation of bacteria. ACS Appl. Mater. Interfaces 2018, 10, 8527–8535. [Google Scholar] [CrossRef]
  97. Sun, Z.; Zhao, Y.; Li, Z.; Cui, H.; Zhou, Y.; Li, W.; Tao, W.; Zhang, H.; Wang, H.; Chu, P.K. as an Efficient Contrast Agent for In Vivo Photoacoustic Imaging of Cancer. Small 2017, 13, 1602896. [Google Scholar] [CrossRef]
  98. Tao, W.; Zhu, X.; Yu, X.; Zeng, X.; Xiao, Q.; Zhang, X.; Ji, X.; Wang, X.; Shi, J.; Zhang, H. Black phosphorus nanosheets as a robust delivery platform for cancer theranostics. Adv. Mater. 2017, 29, 1603276. [Google Scholar] [CrossRef]
  99. Yin, F.; Hu, K.; Chen, S.; Wang, D.; Zhang, J.; Xie, M.; Yang, D.; Qiu, M.; Zhang, H.; Li, Z.-G. Black phosphorus quantum dot based novel siRNA delivery systems in human pluripotent teratoma PA-1 cells. J. Mater. Chem. B 2017, 5, 5433–5440. [Google Scholar] [CrossRef]
  100. Fan, T.; Zhou, Y.; Qiu, M.; Zhang, H. Black phosphorus: A novel nanoplatform with potential in the field of bio-photonic nanomedicine. J. Innov. Opt. Health Sci. 2018, 11, 1830003. [Google Scholar] [CrossRef]
  101. Qiu, M.; Wang, D.; Liang, W.; Liu, L.; Zhang, Y.; Chen, X.; Sang, D.K.; Xing, C.; Li, Z.; Dong, B. Novel concept of the smart NIR-light–controlled drug release of black phosphorus nanostructure for cancer therapy. Proc. Natl. Acad. Sci. USA 2018, 115, 501–506. [Google Scholar] [CrossRef]
  102. Xing, C.; Chen, S.; Qiu, M.; Liang, X.; Liu, Q.; Zou, Q.; Li, Z.; Xie, Z.; Wang, D.; Dong, B. Conceptually novel black phosphorus/cellulose hydrogels as promising photothermal agents for effective cancer therapy. Adv. Healthc. Mater. 2018, 7, 1701510. [Google Scholar] [CrossRef]
  103. Zhou, J.; Li, Z.; Ying, M.; Liu, M.; Wang, X.; Wang, X.; Cao, L.; Zhang, H.; Xu, G. Black phosphorus nanosheets for rapid microRNA detection. Chin. J. Catal. 2018, 10, 5060–5064. [Google Scholar] [CrossRef]
  104. Cho, S.-Y.; Koh, H.-J.; Yoo, H.-W.; Jung, H.-T. Tunable chemical sensing performance of black phosphorus by controlled functionalization with noble metals. Chem. Mater. 2017, 29, 7197–7205. [Google Scholar] [CrossRef]
  105. Li, P.; Zhang, D.; Jiang, C.; Zong, X.; Cao, Y. Ultra-sensitive suspended atomically thin-layered black phosphorus mercury sensors. Biosens. Bioelectron. 2017, 98, 68–75. [Google Scholar] [CrossRef]
  106. Wu, L.; Guo, J.; Wang, Q.; Lu, S.; Dai, X.; Xiang, Y.; Fan, D. Sensitivity enhancement by using few-layer black phosphorus-graphene/TMDCs heterostructure in surface plasmon resonance biochemical sensor. Sens. Actuators B Chem. 2017, 249, 542–548. [Google Scholar] [CrossRef]
  107. Yao, Y.; Zhang, H.; Sun, J.; Ma, W.; Li, L.; Li, W.; Du, J. Novel QCM humidity sensors using stacked black phosphorus nanosheets as sensing film. Sens. Actuators B Chem. 2017, 244, 259–264. [Google Scholar] [CrossRef]
  108. Yew, Y.T.; Sofer, Z.; Mayorga-Martinez, C.C.; Pumera, M. Black phosphorus nanoparticles as a novel fluorescent sensing platform for nucleic acid detection. Mater. Chem. Front. 2017, 1, 1130–1136. [Google Scholar] [CrossRef]
  109. Chen, T.; Zhao, P.; Guo, X.; Zhang, S. Two-fold anisotropy governs morphological evolution and stress generation in sodiated black phosphorus for sodium ion batteries. Nano Lett. 2017, 17, 2299–2306. [Google Scholar] [CrossRef]
  110. Chen, X.; Xu, G.; Ren, X.; Li, Z.; Qi, X.; Huang, K.; Zhang, H.; Huang, Z.; Zhong, J. A black/red phosphorus hybrid as an electrode material for high-performance Li-ion batteries and supercapacitors. J. Mater. Chem. A 2017, 5, 6581–6588. [Google Scholar] [CrossRef]
  111. Cheng, Y.; Zhu, Y.; Han, Y.; Liu, Z.; Yang, B.; Nie, A.; Huang, W.; Shahbazian-Yassar, R.; Mashayek, F. Sodium-induced reordering of atomic stacks in black phosphorus. Chem. Mater. 2017, 29, 1350–1356. [Google Scholar] [CrossRef]
  112. Liu, H.; Tao, L.; Zhang, Y.; Xie, C.; Zhou, P.; Liu, H.; Chen, R.; Wang, S. Bridging covalently functionalized black phosphorus on graphene for high-performance sodium-ion battery. ACS Appl. Mater. Interfaces 2017, 9, 36849–36856. [Google Scholar] [CrossRef]
  113. Liu, H.; Zou, Y.; Tao, L.; Ma, Z.; Liu, D.; Zhou, P.; Liu, H.; Wang, S. Sandwiched thin-film anode of chemically bonded black phosphorus/graphene hybrid for lithium-ion battery. Small 2017, 13, 1700758. [Google Scholar] [CrossRef]
  114. Qiu, M.; Sun, Z.; Sang, D.; Han, X.; Zhang, H.; Niu, C. Current progress in black phosphorus materials and their applications in electrochemical energy storage. Nanoscale 2017, 9, 13384–13403. [Google Scholar] [CrossRef]
  115. Zhao, G.; Wang, T.; Shao, Y.; Wu, Y.; Huang, B.; Hao, X. A Novel Mild Phase-Transition to Prepare Black Phosphorus Nanosheets with Excellent Energy Applications. Small 2017, 13, 1602243. [Google Scholar] [CrossRef]
  116. Luo, S.; Zhao, J.; Zou, J.; He, Z.; Xu, C.; Liu, F.; Huang, Y.; Dong, L.; Wang, L.; Zhang, H. Self-standing polypyrrole/black phosphorus laminated film: Promising electrode for flexible supercapacitor with enhanced capacitance and cycling stability. ACS Appl. Mater. Interfaces 2018, 10, 3538–3548. [Google Scholar] [CrossRef]
  117. He, R.; Hua, J.; Zhang, A.; Wang, C.; Peng, J.; Chen, W.; Zeng, J. Molybdenum disulfide–black phosphorus hybrid nanosheets as a superior catalyst for electrochemical hydrogen evolution. Nano Lett. 2017, 17, 4311–4316. [Google Scholar] [CrossRef]
  118. Lin, Y.; Pan, Y.; Zhang, J. In-situ grown of Ni2P nanoparticles on 2D black phosphorus as a novel hybrid catalyst for hydrogen evolution. Int. J. Hydrogen Energy 2017, 42, 7951–7956. [Google Scholar] [CrossRef]
  119. Dillon, A.C.; Jones, K.; Bekkedahl, T.; Kiang, C.; Bethune, D.; Heben, M. Storage of hydrogen in single-walled carbon nanotubes. Nature 1997, 386, 377–379. [Google Scholar] [CrossRef]
  120. Yildirim, T.; Ciraci, S. Titanium-decorated carbon nanotubes as a potential high-capacity hydrogen storage medium. Phys. Rev. Lett. 2005, 94, 175501. [Google Scholar] [CrossRef]
  121. Kou, L.; Frauenheim, T.; Chen, C. Phosphorene as a superior gas sensor: Selective adsorption and distinct I–V response. J. Phys. Chem. Lett. 2014, 5, 2675–2681. [Google Scholar] [CrossRef]
  122. Cai, Y.; Ke, Q.; Zhang, G.; Zhang, Y.-W. Energetics, charge transfer, and magnetism of small molecules physisorbed on phosphorene. J. Phys. Chem. C 2015, 119, 3102–3110. [Google Scholar] [CrossRef]
  123. Sibari, A.; Kerrami, Z.; Benaissa, M.; Kara, A. Coverage-dependent adsorption of small gas molecules on black phosphorene: A DFT study. Surf. Sci. 2021, 710, 121860. [Google Scholar] [CrossRef]
  124. Li, Q.-F.; Wan, X.; Duan, C.-G.; Kuo, J.-L. Theoretical prediction of hydrogen storage on Li-decorated monolayer black phosphorus. J. Phys. D Appl. Phys. 2014, 47, 465302. [Google Scholar] [CrossRef]
  125. Hassani, N.; Yagmurcukardes, M.; Peeters, F.M.; Neek-Amal, M. Chlorinated phosphorene for energy application. Comput. Mater. Sci. 2024, 231, 112625. [Google Scholar] [CrossRef]
  126. Taylor, P.D.; Tawfik, S.A.; Spencer, M.J. Interplay of mechanical and chemical tunability of phosphorene for flexible nanoelectronic applications. J. Phys. Chem. C 2020, 124, 24391–24399. [Google Scholar] [CrossRef]
  127. Nehra, M.; Dilbaghi, N.; Kumar, R.; Srivastava, S.; Tankeshwar, K.; Kim, K.-H.; Kumar, S. Catalytic applications of phosphorene: Computational design and experimental performance assessment. Crit. Rev. Environ. Sci. Technol. 2024, 54, 185–209. [Google Scholar] [CrossRef]
  128. Plutnar, J.; Šturala, J.; Mazánek, V.; Sofer, Z.; Pumera, M. Fluorination of black phosphorus—Will black phosphorus burn down in the elemental fluorine? Adv. Funct. Mater. 2018, 28, 1801438. [Google Scholar] [CrossRef]
  129. Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50. [Google Scholar] [CrossRef]
  130. Arya, A.; Carter, E.A. Structure, bonding, and adhesion at the TiC (100)/Fe (110) interface from first principles. J. Chem. Phys. 2003, 118, 8982–8996. [Google Scholar] [CrossRef]
  131. Wu, Z.; Cohen, R.E. More accurate generalized gradient approximation for solids. Phys. Rev. B 2006, 73, 235116. [Google Scholar] [CrossRef]
  132. Budimir, M.; Damjanovic, D.; Setter, N. Piezoelectric response and free-energy instability in the perovskite crystals BaTi O3, PbTiO3, and Pb(Zr, Ti)O3. Phys. Rev. B 2006, 73, 174106. [Google Scholar] [CrossRef]
  133. Perdew, J.P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 3865–3868. [Google Scholar] [CrossRef]
  134. Blöchl, P.E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979. [Google Scholar] [CrossRef]
  135. Kresse, G.; Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B Condens. Matter 1999, 59, 1758–1775. [Google Scholar] [CrossRef]
  136. Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186. [Google Scholar] [CrossRef]
  137. Perdew, J.; McMullen, E.; Zunger, A. Density-functional theory of the correlation energy in atoms and ions: A simple analytic model and a challenge. Phys. Rev. A 1981, 23, 2785. [Google Scholar] [CrossRef]
  138. Vanderbilt, D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys. Rev. B 1990, 41, 7892. [Google Scholar] [CrossRef]
  139. Monkhorst, H.J.; Pack, J.D. Special points for Brillouin-zone integrations. Phys. Rev. B 1976, 13, 5188–5192. [Google Scholar] [CrossRef]
  140. Kirklin, S.; Saal, J.E.; Hegde, V.I.; Wolverton, C. High-throughput computational search for strengthening precipitates in alloys. Acta Mater. 2016, 102, 125–135. [Google Scholar] [CrossRef]
  141. Feynman, R.P. Forces in Molecules. Phys. Rev. 1939, 56, 340. [Google Scholar] [CrossRef]
  142. Pham, K.D.; Hoang, T.-D.; Nguyen, Q.-T.; Hoang, D.-Q. Fe-doped SnSe monolayer: A promising 2D material for reusable SO2 gas sensor with high sensitivity. J. Alloys Compd. 2023, 940, 168919. [Google Scholar] [CrossRef]
  143. Hembram, K.; Jung, H.; Yeo, B.C.; Pai, S.J.; Kim, S.; Lee, K.-R.; Han, S.S. Unraveling the atomistic sodiation mechanism of black phosphorus for sodium ion batteries by first-principles calculations. J. Phys. Chem. C 2015, 119, 15041–15046. [Google Scholar] [CrossRef]
  144. Brown, A.; Rundqvist, S. Refinement of the crystal structure of black phosphorus. Acta Crystallogr. 1965, 19, 684–685. [Google Scholar] [CrossRef]
  145. Jiang, J.-W.; Park, H.S. Negative poisson’s ratio in single-layer black phosphorus. Nat. Commun. 2014, 5, 4727. [Google Scholar] [CrossRef]
  146. Jiang, J.-W.; Park, H.S. Mechanical properties of single-layer black phosphorus. J. Phys. D Appl. Phys. 2014, 47, 385304. [Google Scholar] [CrossRef]
  147. Ju, W.; Li, T.; Wang, H.; Yong, Y.; Sun, J. Strain-induced semiconductor to metal transition in few-layer black phosphorus from first principles. Chem. Phys. Lett. 2015, 622, 109–114. [Google Scholar] [CrossRef]
  148. Xu, Y.; Shi, Z.; Shi, X.; Zhang, K.; Zhang, H. Recent progress in black phosphorus and black-phosphorus-analogue materials: Properties, synthesis and applications. Nanoscale 2019, 11, 14491–14527. [Google Scholar] [CrossRef]
  149. Sahin, H.; Ciraci, S. Chlorine adsorption on graphene: Chlorographene. J. Phys. Chem. C 2012, 116, 24075–24083. [Google Scholar] [CrossRef]
Coatings 14 00694 g001
Figure 1. The (a) side view, (b) perspective view, and (c) vertical view of monolayer BP, as well as the lattice constant and P-P bond angle values of pristine BP.
Figure 1. The (a) side view, (b) perspective view, and (c) vertical view of monolayer BP, as well as the lattice constant and P-P bond angle values of pristine BP.
Coatings 14 00694 g001
Coatings 14 00694 g002
Figure 2. Vertical views of three adsorption sites, namely (a) T-site of P atom, (b) H-site, and (c) B-site of the P-P bond. The red atom M represents the decorating halogen atoms (F, Cl, Br, I, and At) on the surface of BP.
Figure 2. Vertical views of three adsorption sites, namely (a) T-site of P atom, (b) H-site, and (c) B-site of the P-P bond. The red atom M represents the decorating halogen atoms (F, Cl, Br, I, and At) on the surface of BP.
Coatings 14 00694 g002
Coatings 14 00694 g003
Figure 3. Front and vertical views of adsorption of gas molecules on surface of BP. The H-sites are taken as an example. (a–c) show that CO2 can exist in three directions, defined as CO2-1, -2, and -3; (d,e) denote that O2 contains two directions, defined as O2-1 and -2, and (f–j) illustrate that H2O has five mode structures, defined as H2O-1, -2, -3, -4, and -5, respectively. Similarly, according to the T- and B-sites, there are a total of 30 gas adsorption models on the BP.
Figure 3. Front and vertical views of adsorption of gas molecules on surface of BP. The H-sites are taken as an example. (a–c) show that CO2 can exist in three directions, defined as CO2-1, -2, and -3; (d,e) denote that O2 contains two directions, defined as O2-1 and -2, and (f–j) illustrate that H2O has five mode structures, defined as H2O-1, -2, -3, -4, and -5, respectively. Similarly, according to the T- and B-sites, there are a total of 30 gas adsorption models on the BP.
Coatings 14 00694 g003
Coatings 14 00694 g004
Figure 4. The front and vertical views of the T-adsorption model are the adsorption of gas molecules based on the BP decorated by the Cl and Br atoms. The green atom X represents Cl and Br atoms. (a–c) show that CO2 exists in three directions, (d,e) illustrate that O2 exists in two directions, and (f–j) denote that H2O has five mode structures.
Figure 4. The front and vertical views of the T-adsorption model are the adsorption of gas molecules based on the BP decorated by the Cl and Br atoms. The green atom X represents Cl and Br atoms. (a–c) show that CO2 exists in three directions, (d,e) illustrate that O2 exists in two directions, and (f–j) denote that H2O has five mode structures.
Coatings 14 00694 g004
Coatings 14 00694 g005
Figure 5. The adsorption energy for (a) halogen atom; (b) CO2 molecule (three directions); (c) O2 molecule (two directions); and (d) H2O molecule (five directions) adsorbed at T-, B-, and H-sites of BP, respectively.
Figure 5. The adsorption energy for (a) halogen atom; (b) CO2 molecule (three directions); (c) O2 molecule (two directions); and (d) H2O molecule (five directions) adsorbed at T-, B-, and H-sites of BP, respectively.
Coatings 14 00694 g005
Coatings 14 00694 g006
Figure 6. The gas adsorbates were at (a) T-, (b) B-, (c) H-sites of BP with the scatter plot of adsorption energy.
Figure 6. The gas adsorbates were at (a) T-, (b) B-, (c) H-sites of BP with the scatter plot of adsorption energy.
Coatings 14 00694 g006
Coatings 14 00694 g007
Figure 7. Scatterplot of adsorption energy for gas adsorption decorated by (a) Cl atom, (b) Br atom on BP at T-sites.
Figure 7. Scatterplot of adsorption energy for gas adsorption decorated by (a) Cl atom, (b) Br atom on BP at T-sites.
Coatings 14 00694 g007
Table 2. The adsorption energy of the adsorbate at the T-, B-, and H-sites of BP.
Table 2. The adsorption energy of the adsorbate at the T-, B-, and H-sites of BP.
AdsorbatesT-Ead (eV)B-Ead (eV)H-Ead (eV)
F−3.11−3.45−3.45
Cl−1.22−1.18−1.18
Br−0.95−0.93−0.92
I−0.40−0.37−0.36
At−0.20−0.18−0.17
CO2-1−0.85−0.44−0.46
CO2-2−0.45−0.45−0.43
CO2-3−0.40−0.61−0.41
H2O-1−0.65−0.45−0.45
H2O-2−0.72−0.50−0.51
H2O-3−0.48−0.48−0.52
H2O-4−0.48−0.45−0.51
H2O-5−0.46−0.48−0.52
O2-1−1.99−0.63−0.58
O2-2−0.59−0.98−1.04
Table 3. Adsorption energy of gas molecules CO2, H2O, and O2 at the T-site of the BP apex decorated by the Cl and Br atoms. The change in distance between the Cl (Br) atom and BP and the change in distance with gas adsorbates also have been listed.
Table 3. Adsorption energy of gas molecules CO2, H2O, and O2 at the T-site of the BP apex decorated by the Cl and Br atoms. The change in distance between the Cl (Br) atom and BP and the change in distance with gas adsorbates also have been listed.
AdsorbatesdCl/Brd0-Cl/Brd0-gasEad (eV)
T-ClCO2-12.242.283.29−1.70
CO2-22.242.262.98−1.50
CO2-32.242.232.88−1.46
H2O-12.242.182.97−1.15
H2O-22.242.293.15−1.48
H2O-32.242.273.17−1.43
H2O-42.242.293.15−1.25
H2O-52.242.273.16−1.36
O2-12.242.272.26−2.03
O2-22.242.272.27−2.09
T-BrCO2-12.472.433.10−1.19
CO2-22.472.503.36−1.37
CO2-32.472.423.03−1.64
H2O-12.472.433.17−1.10
H2O-22.472.503.24−1.14
H2O-32.472.513.23−1.20
H2O-42.472.513.30−1.21
H2O-52.472.523.55−1.23
O2-12.472.502.74−2.00
O2-22.472.502.27−1.95
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Tan, X.; Lin, L.; Fan, T.; Zhang, K. The Effects of Halogen (Cl, Br) Decorating on the Gas Adsorption Behaviors of the Pristine Black Phosphorene: A First-Principles Study. Coatings 2024, 14, 694. https://doi.org/10.3390/coatings14060694

AMA Style

Tan X, Lin L, Fan T, Zhang K. The Effects of Halogen (Cl, Br) Decorating on the Gas Adsorption Behaviors of the Pristine Black Phosphorene: A First-Principles Study. Coatings. 2024; 14(6):694. https://doi.org/10.3390/coatings14060694

Chicago/Turabian Style

Tan, Xinjun, Lan Lin, Touwen Fan, and Kaiwang Zhang. 2024. "The Effects of Halogen (Cl, Br) Decorating on the Gas Adsorption Behaviors of the Pristine Black Phosphorene: A First-Principles Study" Coatings 14, no. 6: 694. https://doi.org/10.3390/coatings14060694

APA Style

Tan, X., Lin, L., Fan, T., & Zhang, K. (2024). The Effects of Halogen (Cl, Br) Decorating on the Gas Adsorption Behaviors of the Pristine Black Phosphorene: A First-Principles Study. Coatings, 14(6), 694. https://doi.org/10.3390/coatings14060694

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop