Capture of pure toxic gases through porous materials from molecular simulations

ABSTRACT

In the last three decades, the air pollution is the main problem to affect human health and the environment in China and its contaminants include SO_2, NH_3, H₂S, NO₂, NO and CO. In this work, we employed grand canonical Monte Carlo simulations to investigate the adsorption capability of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) for these toxic gases. Eighty-nine MOFs and COFs were studied, and top-10 adsorption materials were screened for each toxic gas at room temperature. Dependence of the adsorption performance on the geometry and constructed element of MOFs/COFs was determined and the adsorption conditions were optimised. The open metal sites have mainly influenced the adsorption of NH₃, H₂S, NO₂ and NO. Especially, the X-DOBDC and XMOF-74 (X = Mg, Co, Ni, Zn) series of materials containing open metal sites are all best performance for adsorption of NH₃ to illustrate the importance of electrostatic interaction. Our simulation results also showed that ZnBDC and IRMOF-13 are good candidates to capture the toxic gases NH_3, H₂S, NO₂, NO and CO. This work provides important insights in screening MOF and COF materials with satisfactory performance for toxic gas removal.     

A first-principles study of gas molecule adsorption on hydrogen-substituted graphdiyne

Hydrogen-substituted graphdiyne (HsGDY) is a novel alkynyl carbon material with a structure similar to that of graphene. In this paper, the adsorption of four gas molecules (NO, NO₂, NH₃, and N₂) on HsGDY and B-doped HsGDY (B-HsGDY) was studied using density functional theory. The results show that the adsorption of NO and NO₂ on HsGDY and B-HsGDY is characterized by a larger charge transfer, stronger interaction, and higher adsorption energy compared with that of NH₃ and N₂. Based on the doping with B atoms, the adsorption energies of the gas molecules on HsGDY significantly improve, especially that of NO and NO₂. The gas molecule adsorption on both HsGDY and B-HsGDY is physical adsorption and the adsorption selectivity is good and thus may be applied for gas-sensitive NO and NO₂ materials.     

A first-principle investigation of NO2 adsorption behavior on Co,Rh, and Ir-embedded graphitic carbon nitride: Looking for highly sensitive gas sensor

First-principle calculations were performed to investigate the adsorption behavior of NO₂ gas on the pristine graphitic carbon nitride (gCN) and transition metals (TM)-embedded gCN systems (TM = Co, Rh, and Ir elements) in order to explore the sensing capabilities of gCN systems as toxic gas sensor. The results of adsorption energy revealed that NO₂ gas was physisorbed on the pristine gCN, whereas this gas was strongly chemisorbed on the TM-embedded gCN. Additionally, it was found that the interaction of NO₂ gas with Ir-embedded gCN (−4.47 eV) is much higher than those of the Co and Rh-embedded systems, alluding to its suitability as a highly sensitive gas sensor. The obtained results displayed that the electronic and magnetic properties of the gCN systems remarkably modulated by chemisorption of NO₂ gas. The strong interactions between the TM-embedded gCN and NO₂ gas induced dramatic changes on the conductivity of the systems and led a large reduction in the band gap energy. The results of spin-polarized band structure and density of states indicated that with adsorption of NO₂ gas over the Rh- and Ir-embedded gCN, the magnetic moment of these systems remarkably reduced from 0.10 to 0.07 and 0.01 μB, respectively. Additionally, the results of partial density of states indicated that with adsorption of NO₂ gas over the pristine and TM-embedded gCN systems, the sharp peaks close to the Fermi energy levels of TM-embedded gCN were significantly increased in comparison with the pristine gCN, thanks to the large charge transfer from d-orbitals of the TM atoms to p-orbitals of NO₂ gas. Furthermore, the results of optimized structure showed that with embedding Co-, Rh-, and Ir-elements and also adsorption of NO₂ gas on the gCN, the initial planar structure of the pristine gCN automatically became wrinkle. Finally, based on the obtained results, it can be concluded that the high adsorption energy and considerable charge transfer between NO₂ gas and Ir-embedded gCN make this system as an excellent candidate for NO₂ gas sensor applications.     

A photoelectron spectroscopic observation of iron surfaces exposed to N2, N2O,NO, NO2 and air at 200 torr or 1 atm

Photoelectron spectra from core levels are presented for adsorption of nitrogen-containing gases at 200 torr or 1 atm on iron surfaces. Assignments of each band and the adsorption process are discussed. On the substrate at normal temperature, each gas forms nitride and nitrogen oxide groups (NO, NO₂ and NO₃) which appear at 398.6, 400.0, 404.5 and 407.1 eV, respectively. The relative intensifies of each species depend on the gases adsorbed. NO and NO₂ are considered to dissociate on the surface and the oxygen atom adsorb preferentially. The oxygen on the surface can be considered to contribute to the formation of each surface ligand.     

Mott insulator-superfluid phase transition in p-band triangle optical lattices with on-site rotation

In order to exploit the potential applications of graphene as gas sensors, the adsorptions of a series of small gas molecules (such as CO, O₂, NO₂ and H₂O) on pristine graphene (PG) and Si-doped graphene (SiG) have been investigated by ab initio calculations. Our results indicate that the electronic properties of PG are sensitive to O₂ and NO₂ molecules, but not changed much by the adsorption of CO and H₂O molecules. Compared with PG, SiG is much more reactive in the adsorption of CO, O₂, NO₂ and H₂O. The strong interactions between SiG and the adsorbed molecules induce dramatic changes to the electronic properties of SiG. Therefore, we suggest that SiG could be a good gas sensor for CO, O₂, NO₂ and H₂O.     

Graphene-based nitrogen dioxide gas sensors

In this study, we demonstrated that graphene could selectively absorb/desorb NO_x molecules at room temperature. Chemical doping with NO₂ molecules changed the conductivity of the graphene layers, which was quantified by monitoring the current–voltage characteristics at various NO₂ gas concentrations. The adsorption rate was found to be more rapid than the desorption rate, which can be attributed to the reaction occurred on the surface of the graphene layer. The sensitivity was 9% when an ambient of 100 ppm NO₂ was used. Graphene-based gas sensors showed fast response, good reversibility, selectivity and high sensitivity. Optimization of the sensor design and integration with UV-LEDs and Silicon microelectronics will open the door for the development of nano-sized gas sensors that are extremely sensitive.     

Density functional theory study of NO2-sensing mechanisms of pure and Ti-dopedWO3 （002） surfaces

Density functional theory (DFT) calculations are employed to explore the NO₂-sensing mechanisms of pure and Ti-doped WO₃ (002) surfaces. When Ti is doped into the WO₃ surface, two substitution models are considered: substitution of Ti for W_6c and substitution of Ti for W_5c. The results reveal that substitution of Ti for 5-fold W forms a stable doping structure, and doping induces some new electronic states in the band gap, which may lead to changes in the surface properties. Four top adsorption models of NO₂ on pure and Ti-doped WO₃ (002) surfaces are investigated: adsorptions on 5-fold W (Ti), on 6-fold W, on bridging oxygen, and on plane oxygen. The most stable and likely NO₂ adsorption structures are both N-end oriented to the surface bridge oxygen O_1c site. By comparing the adsorption energy and the electronic population, it is found that Ti doping can enhance the adsorption of NO₂, which theoretically proves the experimental observation that Ti doping can greatly increase the WO₃ gas sensor sensitivity to NO₂ gas.     

Exhaled gas detection by a novel Rh-doped CNT biosensor for prediagnosis of lung cancer: a DFT study

Lung cancer has received considerable attention in recent years due to its high mortality. The difficulty in awareness of such disease can be attributed to its strong insidiousness during the early stage. Therefore, the prognosis of lung cancer becomes significant so as to nip this disease in the bud. In this paper, the Rh-doped CNT-based biosensors were introduced to realise the diagnosis of lung cancer through detecting the exhaled gas of possible patients. The adsorption property and sensing mechanism of Rh-CNT towards two kinds of mainly typical gases of lung cancer, namely, C₆H₆ and C₆H₇N, were analysed based on density functional theory, aiming at evaluating the potential application of such material to be gas sensors. The results indicated that the Rh-CNT not only has good adsorption towards such two gases but also obvious conductivity increase when interacted with any of them, while presents insensitivity upon the common exhaled gas, CO₂. We suggest the Rh-CNT be prepared as biosensors applied in the field of lung cancer pre-diagnosis that can be used in our daily life without pain and complex clinical examination.     

Can bowl-like B30 nanostructure sense toxic cyanogen gas in air?: a theoretical study

In this work, an attempt has been made to study sensing performance of bowl-like B₃₀ nanostructure towards toxic cyanogen gas using density functional theory (DFT) at B97D/6-31+G(d) computational level. The results reveal that B₃₀ nanostructure is a proper sensor for sensing of toxic cyanogen gas. The most favourite adsorption site of B₃₀ is the exterior boron atoms that lead to the adsorption energy of ?78.48 (kJ/mol) with the remarkable change in electronic properties of B₃₀. The competitive sensing of cyanogen gas in the presence of water, oxygen and nitrogen molecules is also considered. Significant changes in the electronic properties of B₃₀ due to adsorption of cyanogen in presence of O₂, H₂O and N₂ gases enable it to be used in the detection of toxic cyanogen gas in air.     

Controlling spin off state by gas molecules adsorption on metal-phthalocyanine molecular junctions and its possibility of gas sensor

Employing Green's function (GF) technique in combination with spin-polarized density functional theory (DFT), we study the electronic structure and magnetic properties of metal phthalocyanine (MPc) (M?=?Mn, Fe, Co, Ni, Cu, Zn) with or without four different gas molecules (NO, CO, O₂ and NO₂) adsorbing on the M atom of MPc molecule. The corresponding stable adsorption structural configurations and transport properties of MPc molecular junctions are also investigated. Our results indicate that the magnetic moment of MPc for M?=?Mn, Fe and Co can be modified by the specific gas molecule adsorption, which is mainly ascribed to competitive relation of HOMO-LUMO Gap and Hund's rules. However, for M?=?Ni, Cu and Zn, it is difficult to detect gas molecule because the interaction of M atom and these gases is most of weak van der Waals interaction. Remarkably, the spin of MPc molecule can be switched to a magnetic off-state by specific gas absorption, giving rise to a potential application on controllable spintronic devices. In addition, CO, NO, O₂ and NO₂ gas molecules can be detected selectively by measuring spin filter efficiency of these MPc molecular junctions. On the basis of our results, MPc (M?=?Mn, Fe, Co) molecular junctions can be considered as a promising nanosensor device to detect individual gas molecules.     

X-ray photoelectron spectroscopic observation of nitrogen-containing gases adsorbed at high pressures on some transition metals

The chemisorbed species formed by reaction of nitrogen-containing gases (NO, N₂O, N₂ and dry air) on some transition metals (Ni, Cu, Ti, Co and Pd) at high pressures (1–200 torr) are examined by XPS. At least four adsorption species are observed on the surface at ambient temperature. They can be assigned to ?NO₃ (407.3 eV), ?NO₂ (404.5 eV), ?NO (400.0 eV) and the nitrogen bound directly to metal, which shows a characteristic energy value for each metal. This feature differs from the reported results of low pressure adsorption experiments. Relative abundances among the chemisorbed species vary with individual metals and gases.     

V掺杂二维MoS_2体系气体吸附性能的第一性原理研究

以芥子气和沙林为代表的毒剂具有毒性强、扩散快的特点,是一类杀伤力强、难以防护的化学战剂,对其快速高效检测是一项具有挑战性的课题.本文基于第一性原理计算方法研究了V掺杂对二维MoS_2气敏性能影响的机理,发现V原子向二维MoS_2的掺杂过程为自发的放热反应, V原子可以稳定掺杂于二维MoS_2超胞结构中的S空位上.掺杂进入二维MoS_2体系的V原子作为施主中心向周围Mo原子给出电子,从而提高了材料的导电能力.吸附能、吸附距离和吸附过程中的电子转移计算结果表明V的掺杂提高了二维MoS_2对气体分子的吸附能力,增强了吸附质分子与基底表面的电子相互作用,从而提高了二维MoS_2的气敏性能.     

Coadsorption of NO and other small gases (H2 and CO) on polycrystalline rhodium surface

The coadsorption of NO and other small gases (H₂ and CO) on a polycrystalline Rh filament has been studied by thermal desorption mass spectroscopy, using ¹⁵NO. The sample was exposed to a mixture of nitric oxide and other gases with various concentrations of ¹⁵NO at room temperature. It is indicated that NO, CO and H₂ coadsorbs on the rhodium surface, and NO desorbs as N₂ and O₂. NO is adsorbed mainly in the dissociation at lower coverage and molecular adsorption becomes dominant at higher coverage. But the amount of desorbed O₂ was very small. The chemisorption of CO is affected by the chemisorbed NO. Thermal desorption of hydrogen is detected when the value of P_15NO/P_CO is very small. The hydrogen adsorbed on the rhodium surface is replaced by NO with a longer exposure time.     

Determination of H2S,COS, CS2 and SO2 by an aluminium nitride nanocluster: DFT studies

ABSTRACT

Density functional theory calculations were used to investigate the potential application of an AlN nanocluster in the detection of H₂S, COS, CS₂ and SO₂ gases. In overall, the order of strength of interaction of these gases with the nanocluster is as follows: SO₂ (E_ad?=??17.6?kcal/mol)?>?H₂S (E_ad?=??14.0?kcal/mol)?>?COS (E_ad?=??8.4?kcal/mol)?>?CS₂ (E_ad?=??4.5?kcal/mol). This indicates that by increasing the electric dipole moment, the adsorption energy becomes more negative. We found that the Al₁₂N₁₂ nanocluster may be a promising work function-type sensor for SO₂ gas among the studied gases. Also, it is an electronic sensor for both SO₂ and CS₂ gases but selectively acts between them because of their different effects on the electrical conductivity. It is neither work function-type nor electronic sensor for H₂S and COS gases. The AlN nanocluster benefits from a short recovery time about 7.7?s and 18.0?ms for desorption of SO₂ and CS₂ gases from its surface at room temperature, respectively. It is also concluded that this cluster can work at a humid environment.     

Adsorption of small molecules on transition metal doped rhodium clusters Rh3X (X = 3d, 4d atom): a first-principles investigation

The adsorption behaviours of seven molecules (CO, CO₂, N₂, NO, O₂, N₂O and NO₂) on Rh₃X (X?=Sc-Zn, Y-Cd) clusters are systematically investigated by density-functional calculations. Rh₃X clusters exhibit physical adsorption when interacting with CO₂, CO, N₂ and NO. The adsorption energies (E_ads) can be ranked as follows: NO?>?CO?>?CO_2?≥?N₂. Compared with pure Rh₄ cluster, the adsorption capacity changes with the doping element. Chemical adsorption can be obtained for Rh₃X when adsorbing O₂, N₂O and NO₂. E_ads shows an order of E_ads(O₂)?>?E_ads(NO₂)?>?E_ads(N₂O). When O₂ is adsorbed, energy barrier with doping Tc or Cr atom is substantially reduced, which indicates that chemical reactivity of O₂ on Rh₄ can be significantly enhanced. The doped rhodium clusters can be viewed as good candidates in the discrimination between different gas molecules.     

SERS and XPS observation of the adsorption behavior of NO and NO2 on a silver powder surface

The influence of H₂O on the adsorption behavior of NO or NO₂ on a silver powder surface was studied by SERS and XPS at room temperature. Water vapor was found to be responsible for the adsorption of NO on the silver powder surface. When surface species such as Ag₂O are present on the surface, some of the NO₂ molecules are adsorbed on the surface species to produce NO^-₃, whereas NO molecules are adsorbed on a different site to produce NO^-₂.     

Photoconductivity and dark conductivity of hydrogenated amorphous silicon

The study of plasma-deposited hydrogenated amorphous silicon films prepared in various deposition systems and under the use of different gases (SiH₄, SiD₄, Si₂H₄) shows a unique correlation between the photoconductivity and the dark conductivity of undoped and lightly doped films grown under optimized conditions. Deviations from his relation occur at high doping levels, in particular for boron doping, as well as upon annealing. They are attributed to an increased density of gap states due to hydrogen depletion.     

Adsorption behaviour of SF6 decomposed species onto Pd4-decorated single-walled CNT: a DFT study

Metal nanocluster decorated single-walled carbon nanotubes (SWCNT) with improved adsorption behaviour towards gaseous molecules compared with intrinsic ones, have been widely accepted as a workable media for gas interaction due to their strong catalysis. In this work, Pd₄ cluster is determined as a catalytic centre to theoretically study the adsorption property of Pd₄-decorated SWCNT upon SF₆ decomposed species. Results indicate that Pd₄-SWCNT possessing good responses and sensitivities towards three composed species of SF₆ could realise selective detection for them according to the different conductivity changes resulting from the varying adsorption ability. The response of Pd₄-SWCNT upon three molecules in order is SOF₂ > H₂S > SO₂, and the conductivity of the proposed material is about to increase in SOF₂ and H₂S systems, while declining in SO₂ system. Such conclusions would be helpful for experimentalists to explore novel SWCNT-based sensors in evaluating the operating state of SF₆ insulation devices.     

Friction behavior of monolayer molybdenum diselenide nanosheet under normal electric field

The friction behavior of monolayer molybdenum diselenide (MoSe₂) under normal electric field was studied by the atomic force microscope. The friction coefficients of MoSe₂ are increasing with bias voltage applied on the Si substrate. The results show that the adhesion and electrostatic forces increase with bias and approximately follow a parabolic law. The friction force and surface potential are of the same tendency with bias application time, and the contribution of charges accumulation to friction is considerable. The mechanisms of the friction behavior under external normal electric field were explained with electrostatic force and adsorption. This study reveals a possibility of electronically controlling friction in two-dimensional MoSe₂ system, with potential applications in solid lubricant and moving parts for MEMS devices.