Adsorption Characteristics and Mechanism of Calcium Ions on Different Molybdenite Surfaces via Experiments and DFT Simulations
TL;DR: In this paper, various methods including flotation tests, contact angle measurements, batch adsorption tests and Density Functional Theory (DFT) simulations were carried out to understand the adaption characteristics and mechanism.
Abstract: Calcium ions are common in flotation process water, and have a significant effect on the molybdenite floatability, making separation of molybdenite from other minerals more difficult. Therefore, to improve the separation selectivity, the research of how calcium ions affect the molybdenite surface properties is of great significance. In this study, various methods including flotation tests, contact angle measurements, batch adsorption tests and Density Functional Theory (DFT) simulations were carried out to understand the adsorption characteristics and mechanism. Results of the contact angle measurements showed that the inhibition effects of calcium ions on molybdenite flotation kinetics were mostly attributed to the decrease of the edge surface hydrophobicity, as the contact angle of the edge surface decreased more than the face surface after treatment with calcium ions. While fitting the results of batch adsorption tests with adsorption kinetics and isotherm models, it was found that the Lagergen pseudo-first-order equation and the Freundlich isotherm model nicely follow the experimental trend. Moreover, DFT calculation results indicated that both Ca2+ and CaOH+ preferentially adsorb on the molybdenite (100) surface, particularly the edge surface, which was consistent with the contact angle results. Ca2+ adsorbed on the Mo-top site on the S-(100) surface by forming Ca-S bonds, transferring electrons from Ca 3d orbitals to S 3p orbitals. CaOH+ adsorbed on the S-top site of Mo-(100) surface by forming a strong covalent Mo-O bond and S-Ca bond. The results provide a basis for understanding and improving the separation effect of molybdenite from other minerals in the presence of calcium ions.
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TL;DR: In this paper, density functional theory (DFT) calculation was taken to investigate the adsorption of reagents from the atomic and electronic microscopic perspective, and the activation mechanism of calcium was discovered.
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TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
Abstract: Generalized gradient approximations (GGA’s) for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental constants. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential. [S0031-9007(96)01479-2] PACS numbers: 71.15.Mb, 71.45.Gm Kohn-Sham density functional theory [1,2] is widely used for self-consistent-field electronic structure calculations of the ground-state properties of atoms, molecules, and solids. In this theory, only the exchange-correlation energy EXC › EX 1 EC as a functional of the electron spin densities n"srd and n#srd must be approximated. The most popular functionals have a form appropriate for slowly varying densities: the local spin density (LSD) approximation Z d 3 rn e unif
146,533 citations
TL;DR: The ability of different metal surfaces and of the enzymes nitrogenase and hydrogenase to catalyze the hydrogen evolution reaction is analyzed and a necessary criterion for high catalytic activity is found: that the binding free energy of atomic hydrogen to the catalyst is close to zero.
Abstract: The electrochemical hydrogen evolution reaction is catalyzed most effectively by the Pt group metals. As H2 is considered as a future energy carrier, the need for these catalysts will increase and alternatives to the scarce and expensive Pt group catalysts will be needed. We analyze the ability of different metal surfaces and of the enzymes nitrogenase and hydrogenase to catalyze the hydrogen evolution reaction and find a necessary criterion for high catalytic activity. The necessary criterion is that the binding free energy of atomic hydrogen to the catalyst is close to zero. The criterion enables us to search for new catalysts, and inspired by the nitrogenase active site, we find that MoS2 nanoparticles supported on graphite are a promising catalyst. They catalyze electrochemical hydrogen evolution at a moderate overpotential of 0.1−0.2 V.
3,302 citations
TL;DR: This first study comparing the two surfaces of MoS2 by using macroscopic crystals with precise control over the exposure of one plane surface is presented, and the experimental comparison of the edge and basal planes ofMoS2 crystals is supported by DFT calculations.
Abstract: The layered structure of molybdenum disulfide (MoS2 ) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2 : basal and edge planes. The edge plane was theoretically predicted to be more electroactive than the basal plane, but evidence from direct experimental comparison is elusive. Herein, the first study comparing the two surfaces of MoS2 by using macroscopic crystals is presented. A careful investigation of the electrochemical properties of macroscopic MoS2 pristine crystals with precise control over the exposure of one plane surface, that is, basal plane or edge plane, was performed. These crystals were characterized thoroughly by AFM, Raman spectroscopy, X-ray photoelectron spectroscopy, voltammetry, digital simulation, and DFT calculations. In the Raman spectra, the basal and edge planes show anisotropy in the preferred excitation of E2g and A1g phonon modes, respectively. The edge plane exhibits a much larger heterogeneous electron transfer rate constant k(0) of 4.96×10(-5) and 1.1×10(-3) cm s(-1) for [Fe(CN)6 ](3-/4-) and [Ru(NH3 )6 ](3+/2+) redox probes, respectively, compared to the basal plane, which yielded k(0) tending towards zero for [Fe(CN)6 ](3-/4-) and about 9.3×10(-4) cm s(-1) for [Ru(NH3 )6 ](3+/2+) . The industrially important hydrogen evolution reaction follows the trend observed for [Fe(CN)6 ](3-/4-) in that the basal plane is basically inactive. The experimental comparison of the edge and basal planes of MoS2 crystals is supported by DFT calculations.
127 citations
TL;DR: In this article, the applicability of isotherm models to a group of adsorbent-adsorbate systems was studied and the correlating ability of the various models was compared in terms of arithmetic average relative deviation calculated based on qe.
83 citations
TL;DR: This is the first study in directly measuring surface charge and wettability of the pristine face and edge surfaces of molybdenite through surface force measurements and the results suggest the hydrophobic feature of the face surface of molenite.
Abstract: Probing anisotropic surface properties of layer-type mineral is fundamentally important in understanding its surface charge and wettability for a variety of applications. In this study, the surface properties of the face and the edge surfaces of natural molybdenite (MoS2) were investigated by direct surface force measurements using atomic force microscope (AFM). The interaction forces between the AFM tip (Si3N4) and face or edge surface of molybdenite were measured in 10 mM NaCl solutions at various pHs. The force profiles were well-fitted with classical DLVO (Derjaguin-Landau-Verwey-Overbeek) theory to determine the surface potentials of the face and the edge surfaces of molybdenite. The surface potentials of both the face and edge surfaces become more negative with increasing pH. At neutral and alkaline conditions, the edge surface exhibits more negative surface potential than the face surface, which is possibly due to molybdate and hydromolybdate ions on the edge surface. The point of zero charge (PZC) of the edge surface was determined around pH 3 while PZC of the face surface was not observed in the range of pH 3-11. The interaction forces between octadecyltrichlorosilane-treated AFM tip (OTS-tip) and face or edge surface of molybdenite were also measured at various pHs to study the wettability of molybdenite surfaces. An attractive force between the OTS-tip and the face surface was detected. The force profiles were well-fitted by considering DLVO forces and additional hydrophobic force. Our results suggest the hydrophobic feature of the face surface of molybdenite. In contrast, no attractive force between the OTS-tip and the edge surface was detected. This is the first study in directly measuring surface charge and wettability of the pristine face and edge surfaces of molybdenite through surface force measurements.
62 citations