Theoretical and Experimental Researches of Size-Dependent Surface Thermodynamic Properties of Nanovaterite

Zhang, Zhi; Fu, Qingshan; Xue, Yongqiang; Wang, Shanshan

doi:10.1021/acs.jpcc.6b07429

Cited by 27 publications

(8 citation statements)

References 32 publications

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“…56 The surface energy of nano-CdS is large, and results in a decrease in Gibbs free energy during the process of dissolution, thus leading to the increased standard dissolution equilibrium constant with decreasing particle size during dissolution. 80 4.3 Influence of particle size on the standard molar dissolution thermodynamic functions 4.3.1 Influence of particle size on the standard molar dissolution Gibbs free energy. Eqn (22) was used to calculate the standard molar dissolution Gibbs free energy of nano-CdS with different particle sizes.…”

Section: Influence Of Particle Size On the Standard Dissolution Equil...mentioning

confidence: 99%

Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies

Zhang

Tan

Zhou

et al. 2022

Phys. Chem. Chem. Phys.

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Section: Influence Of Particle Size On the Standard Dissolution Equil...mentioning

confidence: 99%

Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies

Zhang

Tan

Zhou

et al. 2022

Phys. Chem. Chem. Phys.

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“…For the adsorption of spherical nanoparticles without holes, the partial molar surface Gibbs free energy (surface chemical potential) is equal to the molar surface Gibbs free energy, that is where σ N , r , and V N are the surface tension, radius, and molar volume of the nanoparticles, respectively.…”

Section: Nanoadsorption Theorymentioning

confidence: 99%

Section: Nanoadsorption Theorymentioning

confidence: 99%

“…Previously, our group developed the size-dependent thermodynamics of nanoadsorption to understand the general adsorption regularities. 22 However, the definitions of the chemical potentials of the surface phases of both the nanoparticles 28 and the adsorption product are not exact, and the standard state of chemical potential of adsorption product is defined as the saturated state, such that the thermodynamic equations derived are only applicable to the saturated state. Thus, we have sought to solve these problems in this study.…”

Section: Introductionmentioning

confidence: 99%

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Size-Dependent Thermodynamics and Kinetics of Adsorption on Nanoparticles: A Theoretical and Experimental Study

et al. 2018

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Owing to their excellent adsorption properties compared with those of the corresponding bulk materials, nanoparticles have been widely applied in many fields. Their properties depend on the thermodynamics and kinetics of adsorption, which depend on the particle size. In this paper, we present universal theories of the thermodynamics and kinetics for nanoadsorption that have been developed over the past few years. Theoretically, we have derived relationships between the adsorption thermodynamic properties and the particle size, as well as those between the adsorption kinetic parameters and the particle size. Moreover, we discuss the regularities and mechanisms of influence of the particle size on the thermodynamics and kinetics of adsorption. Experimentally, taking the adsorption of methyl orange on nano-CeO in aqueous solution as a system, we have studied the size-dependent thermodynamics and kinetics of the system, and the size dependences were confirmed to be consistent with the theoretical relationships. The results indicate that particle size has a significant effect on the thermodynamic properties and kinetic parameters of adsorption: with decreasing particle size of nano-CeO, the adsorption equilibrium constant K and the adsorption rate constant k increase, while the molar Gibbs free energy of adsorption Δ G, the molar adsorption entropy Δ S, the molar adsorption enthalpy Δ H, the adsorption activation energy E, and the adsorption pre-exponential factor A all decrease. Indeed, ln K, Δ G, Δ S, Δ H, ln  k, E, and ln  A are each linearly related to the reciprocal of particle size. Furthermore, thermodynamically, Δ G and ln  K are influenced by the molar surface area and the difference in surface tensions, Δ S is influenced by the molar surface area and the difference in temperature coefficients of surface tension, and Δ H is influenced by the molar surface area, the difference in surface tensions, and the difference in temperature coefficients of surface tension. Kinetically, E is influenced by the partial molar surface enthalpy of the nanoadsorbent, ln  A is influenced by the partial molar surface entropy, and ln  k is influenced by the partial molar surface Gibbs energy. The theories can quantitatively describe adsorption behavior on nanoparticles, explain the regularities and mechanisms of influence of particle size, and provide guidance for the research and application of nanoadsorption.

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“…For general metal nanoparticles, the orders of magnitude for σ, V , α, T , and

{(\partial σ / \partial T)}_{normalp}

are 10 −1 –10 0 J m −2 , 10 −5 m 3 mol −1 ,10 −5 , 10 2 K, and 10 −4 J m −2 K −1 , respectively. It can be deduced that both partial molar surface area (2 V m / r ) and surface tension are major influencing factors for the melting temperature of nanoparticles; molar surface area (3 V m / r ) and surface tension are for the integral melting enthalpy of nanoparticles; while molar surface area and the temperature coefficient of surface tension are for the integral melting entropy.…”

Section: Theoretical Sectionmentioning

confidence: 99%

Influence of Size on Melting Thermodynamics of Nanoparticles: Mechanism, Factors, Range, and Degree

Duan

Xue

Cui

et al. 2018

Part & Part Syst Charact

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Particle size plays a crucial role in melting process of nanoparticles, but the mechanism, factors, range, and degree of the size effect are still unclear. Here, the precise equations of the integral melting enthalpy and entropy with radius of nanoparticles are deduced, without any adjustable parameters, and the influencing mechanism and the factors are discussed. Experimentally, the melting of spherical nano‐Au with different radii (0.9–37.4 nm) is taken as a system to research the melting behavior of nanoparticles. Combining the results of theory and experiments, the influencing regularities, range, and degree are discussed. The results indicate that there are significant effects of particle size on the temperature, integral enthalpy, and integral entropy of melting, which decrease with the radius decreasing. These effects can be attributed to specific surface area, surface tension, and its temperature coefficient. When the radius exceeds 10 nm, specific surface area is the decisive factor, there exists the linear relationships of temperature, integral enthalpy, and integral entropy of melting with the reciprocal of radius. However, when the radius is less than 10 nm, the effects of surface tension and its temperature coefficient gradually hold the main position, the linear relations do not exist.

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Theoretical and Experimental Researches of Size-Dependent Surface Thermodynamic Properties of Nanovaterite

Cited by 27 publications

References 32 publications

Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies

Critical size effect for the surface heat capacities of nano-CdS: theoretical and experimental studies

Size-Dependent Thermodynamics and Kinetics of Adsorption on Nanoparticles: A Theoretical and Experimental Study

Influence of Size on Melting Thermodynamics of Nanoparticles: Mechanism, Factors, Range, and Degree

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