Surface Hydration Research Articles

Promotion Mechanism of Ammonium Formate in Ammonium Salt Leaching Process for Weathered Crust Elution-Deposited Rare Earth Ores

Weathered crust elution-deposited rare earth ores (WREOs) are significant strategic mineral resources. In industry, in situ leaching technology is usually applied with ammonium chloride and ammonium sulfate as the leaching solution. However, the slow seepage velocity of the leaching solution and low rare earth leaching efficiency still need to be improved. Ammonium formate can effectively improve the WREO leaching process. In order to further explore the effects of ammonium formate on the ammonium salt leaching process for WREOs, ammonium chloride and ammonium sulfate compounded with ammonium formate were used as leaching agents to determine their effects on leaching efficiency, seepage velocity and swelling. The results show that in the presence of ammonium formate, the rare earth leaching efficiencies with ammonium chloride and ammonium sulfate are both slightly increased, the seepage velocity of ammonium chloride and ammonium sulfate is increased by 1.67 × 10−4 cm·s−1 and 1.18 × 10−4 cm·s−1, and the swelling percentage falls by 0.14% and 0.37%, respectively. The thickness of the adsorbed water layer and thermogravimetric and XRD results confirm that ammonium formate can inhibit surface hydration and thus improve the WREO leaching process.

Biodeterioration and Chemical Corrosion of Concrete in the Marine Environment: Too Complex for Prediction.

Concrete is the most utilized construction material worldwide. In the marine environment, it is subject to chemical degradation through reactions with chloride (the most important ion), and sulfate and magnesium ions in seawater, and to biodeterioration resulting from biological (initially microbiological) activities, principally acid production. These two types of corrosions are reviewed and the failure of attempts to predict the degree of deterioration resulting from each is noted. Chemical (abiotic) corrosion is greatest in the splash zone of coastal constructions, while phenomenological evidence suggests that biodeterioration is greatest in tidal zones. There have been no comparative experiments to determine the rates and types of microbial biofilm formation in these zones. Both chemical and microbiological concrete deteriorations are complex and have not been successfully modeled. The interaction between abiotic corrosion and biofilm formation is considered. EPS can maintain surface hydration, potentially reducing abiotic corrosion. The early marine biofilm contains relatively specific bacterial colonizers, including cyanobacteria and proteobacteria; these change over time, producing a generic concrete biofilm, but the adhesion of microorganisms to concrete in the oceans has been little investigated. The colonization of artificial reefs is briefly discussed. Concrete appears to be a relatively prescriptive substrate, with modifications necessary to increase colonization for the required goal of increasing biological diversity.

Experimental study of the formation and decomposition of mixed gas hydrates in water-hydrocarbon system

The phase transition of gas hydrate with two or more guests is associated with gas recovery, storage and separation. In this work, the formation and decomposition of binary and ternary gas hydrates containing CH4, C2H6 and C3H8 were investigated experimentally in high-pressure reactors equipped with visual windows. The gas compositions during mixed hydrates formation and decomposition were analyzed to track the occupation of guests in hydrate structures and the release of guests from hydrate cages. It was found that of CH4 was adsorbed in the hydrate cages constructed by C2H6 and C3H8 in the initial stage. In the depressurized decomposition of CH4-C3H8 hydrates and CH4-C2H6-C3H8 hydrates slurry, CH4 and C2H6 molecules were preferentially released from hydrate structures while more C3H8 molecules were able to stay in hydrate phase, which was in accordance with the order of the diameter ratio of guest molecule to hydrate cage. The preservation of CH4-C3H8 hydrates and CH4-C2H6-C3H8 hydrates above 0 ℃ was observed under a low pressure. It was proposed that the reconstitution or reformation of hydrate layer rich of C3H8 may encrust the remaining hydrate particles, preventing hydrate from further quick decomposition. In-situ Raman spectra confirmed the enrichment of C3H8 molecules at the surface of CH4-C3H8 hydrates, which revealed that the metastable hydrate layer rich of C3H8 molecules may act as mass transfer resistance of gas release from hydrate decomposition. Differently, the decompositions of CH4-C2H6 hydrates and C2H6-C3H8 hydrates were uniform as different guests were produced concurrently without preservation. The new insights into mixed hydrates decomposition in this work may provide a new basis for mixed gas production from gas hydrate, and gas storage and separation with hydrate.

Characterization of the quasi-liquid layer on gas hydrates with molecular dynamics simulations

Understanding the properties of the surficial quasi-liquid layer (QLL) is a prerequisite in proper handling of gas hydrates, a potential alternative future energy resource. Despite of its critical importance, the characterization of QLL has long been known to be highly challenging. In this work, the evolution of QLL during hydrate decomposition was systematically investigated by Molecular Dynamics simulations. Using the instant displacement of water molecules as a measure of the fluidity of the molecular layer adjacent to hydrate surfaces, QLL thickness was accurately measured using the dynamic properties of water molecules for the first time. The QLL thickness obtained by this new molecular dynamics-based approach takes amorphous water molecules close to hydrate surfaces into account, which was often ignored in the previous results based on the static structural order parameters. The variation of QLL thickness throughout the hydrate decomposition process at different temperatures and pressures was then evaluated. The thickness of QLL was found to increase with elevated temperature and pressure, owing to the varied changes of the amorphous and hydrate-like molecular content in this important layer. The results regarding the dynamics of the QLL with molecular resolution improved the current understanding on the stability of gas hydrate and shed new light on the physical fundamentals relevant to future hydrate exploration as well as anti-hydrate materials design.

Tracking of Protein Adsorption on Poly(l-lactic acid) Film Surfaces: The Role of Molar Mass.

Poly(l-lactic acid) (PLLA) has been extensively utilized as a biomaterial for various biomedical applications. The first and one of the most critical steps upon contact with biological fluids is the adsorption of proteins on the material's surface. Understanding the behavior of protein adsorption is vital for guiding the synthesis and preparation of PLLA for biomedical purposes. In this study, total internal reflection fluorescence microscopy was employed to investigate the adsorption of human serum albumin (HSA) on PLLA films with different molar masses. We found that molar mass affects HSA adsorption in such a way that it affects only the adsorption rate constants, but not the desorption rate constants. Additionally, we observed that HSA adsorption is spatially heterogeneous and exhibits many strong binding sites regardless of the molar mass of the PLLA films. We found that the free volume of PLLA plays a crucial role in determining its water uptake capacity and surface hydration, consequently impacting the adsorption of HSA.

Atomic-Level and Surface Structure of Calcium Silicate Hydrate Nanofoils.

Deciphering the calcium silicate hydrate (C-S-H) surface is crucial for unraveling the mechanisms of cement hydration and property development. Experimental observations of C-S-H in cement systems suggest a surface termination which is fundamentally different from the silicate-terminated surface assumed in many atomistic level studies. Here, a new multiparameter approach to describing the (001) basal C-S-H surface is developed, which considers how the surface termination affects the overall properties (Ca/Si ratio, mean chain length, relative concentration of silanol and hydroxide groups). Contrary to current beliefs, it is concluded that the (001) C-S-H surface is dominantly calcium terminated. Finally, an adsorption mechanism for calcium and hydroxide ions is proposed, which is in agreement with the surface charge densities observed in previous studies.

Different pathways to anomalous stabilization of ice layers on methane hydrates.

We explore the Casimir-Lifshitz free-energy theory for surface freezing of methane gas hydrates near the freezing point of water. The theory enables us to explore different pathways, resulting in anomalous (stabilizing) ice layers on methane hydrate surfaces via energy minimization. Notably, we will contrast the gas hydrate material properties, under which thin ice films can form in water vapor, with those previously predicted to be required in the presence of liquid water. It is predicted that methane hydrates in water vapor near the freezing point of water nucleate ice films, instead of water films.

Cyclopentane hydrate wettability measurements used to evaluate the efficacy of oil natural surfactants using ultra-low volume samples

Hydrate surface wettability is a fundamental aspect to better understand agglomeration present in oil bearing petroleum pipelines. Coupling these measurements with hydrate film growth gives further information on kinetic effects that may also be present from natural surfactants in different oils. In situ measurements of wettability (quantified by the contact angle) and film growth rates were performed on cyclopentane hydrate surfaces at atmospheric pressure and subcooling of 4 °C. Contact angle and film growth results were obtained for the baseline system (pure cyclopentane), one model oil, and seventeen natural oils (diluted to 0.02 vol% in cyclopentane). Results showed a wide variety of contact angles and film growth values where higher asphaltene contents in the oils corresponded to higher contact angles and lower film growth rates, thought to be from better alignment of natural surfactant molecules at the hydrate/hydrocarbon interface. It was also shown for select oils that increasing the oil concentration in the cyclopentane increases the contact angle and decreases the film growth rate compared to the baseline system. For select oils that had higher contact angles, increasing the water content of the system decreases their contact angle and film growth compared to the baseline system. Isolating different oil fractions for select oils also shows which fractions tend to play a larger role in wettability behavior. Typically, the fractions with more surface active components (asphaltene and resins) are shown to contribute to the higher contact angle and slower film growth rates for select oils. Evidence of the competition between film growth and capillary suction of water into the hydrate has been shown, and a mechanistic breakdown of three different transient scenarios has been proposed. Each of these observed interfacial behaviors gives information on what can be expected from larger scale phenomena, including hydrate agglomeration, with very small oil samples.

A novel salt- and organic solvent-tolerant phosphite dehydrogenase from Cyanothece sp. ATCC 51142.

Phosphite dehydrogenase (PtxD) is a promising enzyme for NAD(P)H regeneration. To expand the usability of PtxD, we cloned, expressed, and analyzed PtxD from the marine cyanobacterium Cyanothece sp. ATCC 51142 (Ct-PtxD). Ct-PtxD exhibited maximum activity at pH 9.0°C and 50°C and high stability over a wide pH range of 6.0-10.0. Compared to previously reported PtxDs, Ct-PtxD showed increased resistance to salt ions such as Na+, K+, and NH4 +. It also exhibited high tolerance to organic solvents such as ethanol, dimethylformamide, and methanol when bound to its preferred cofactor, NAD+. Remarkably, these organic solvents enhanced the Ct-PtxD activity while inhibiting the PtxD activity of Ralstonia sp. 4506 (Rs-PtxD) at concentrations ranging from 10% to 30%. Molecular electrostatic potential analysis showed that the NAD+-binding site of Ct-PtxD was rich in positively charged residues, which may attract the negatively charged pyrophosphate group of NAD+ under high-salt conditions. Amino acid composition analysis revealed that Ct-PtxD contained fewer hydrophobic amino acids than other PtxD enzymes, which reduced the hydrophobicity and increased the hydration of protein surface under low water activity. We also demonstrated that the NADH regeneration system using Ct-PtxD is useful for the coupled chiral conversion of trimethylpyruvic acid into L-tert-leucine using leucine dehydrogenase under high ammonium conditions, which is less supported by the Rs-PtxD enzyme. These results imply that Ct-PtxD might be a potential candidate for NAD(P)H regeneration in industrial applications under the reaction conditions containing salt and organic solvent.

Effect of hydroxide, carbonate, and sulphate anions on the β-dicalcium silicate hydration rate

The effect of fixed (0.8 M) Na+ balanced by either OH−, SO42−, and CO32− anions on β-dicalcium silicate (C2S) reactivity is investigated. The exothermic reaction of varying water-to-solid ratios and chemical activation is monitored. Subsequently, the hydration products are characterized via FTIR, TG/DTG, QXRD, and SEM analysis. The findings showed that the carbonate ions expedited the reactivity up to 55% at 1–7 days due to the simultaneous precipitation of calcium silicate hydrate (C-S-H) and calcite. At 7–28 days, the lack of transportable cations between the solid surface and solution impeded further hydration, as confirmed by in-situ pH and conductivity measurements. The sulphate ions accelerated the reactivity only upon calcium sulphate dissolution at high pH. The hydroxide ions decelerated the hydration due to the earlier precipitation of portlandite than C-S-H. Overall, the β-C2S reaction with water exhibited the highest hydration degree (~67%) after 28 days of hydration.

Solvatochromic and Acid–Base Molecular Probes in Surfactant Micelles: Comparison of Molecular Dynamics Simulation with the Experiment

This article summarizes a series of seventeen publications by the authors devoted to molecular dynamics modeling of various indicator dyes (molecular probes) enclosed in surfactant micelles. These dyes serve as generally recognized tools for studying various types of organized solutions, among which surfactant micelles in water are the simplest and most explored. The modeling procedure involves altogether 50 to 95 surfactant molecules, 16 to 28 thousand water molecules, and a single dye molecule. The presentation of the simulation results was preceded by a brief review of the state of experimental studies. This article consists of three parts. First, despite numerous literature data devoted to modeling the micelles itself, we decided to revisit this issue. The structure and hydration of the surface of micelles of surfactants, first of all of sodium n-dodecylsulfate, SDS, and cetyltrimethylammonium bromide, CTAB, were studied. The values of the electrical potential, Ψ, were estimated as functions of the ionic strength and distance from the surface. The decrease in the Ψ value with distance is gradual. Attempts to consider both DS− and CTA+ micelles in water without counterions result in a decay into two smaller aggregates. Obviously, the hydrophobic interaction (association) of the hydrocarbon tails balances the repulsion of the charged headgroups of these small “bare” micelles. The second part is devoted to the study of seven pyridinium N-phenolates, known as Reichardt’s dyes, in ionic micelles. These most powerful solvatochromic indicators are now used for examining various colloidal systems. The localization and orientation of both zwitterionic and (colorless) cationic forms are generally consistent with intuitive ideas about the hydrophobicity of substituents. Hydration has been quantitatively described for both the dye molecule as a whole and the oxygen atom. A number of markers, including the visible absorption spectra of Reichardt’s dyes, enable assuming a better hydration of the micellar surface of SDS than that of CTAB. However, our data show that it is more correct to speak about the more pronounced hydrogen-bonding ability of water molecules in anionic micelles than about better hydration of the SDS micelles as compared to CTAB ones. Finally, a set of acid–base indicators firmly fixed in the micellar pseudophase were studied by molecular dynamics. They are instruments for estimating electrostatic potentials of micelles and related aggregates as Ψ= 2.303RTF−1 (pKai − pKaapp), where pKai and pKaapp are indices of so-called intrinsic and apparent dissociation constants. In this case, in addition to the location, orientation, and hydration, the differences between values of pKaapp and indices of the dissociation constants in water were estimated. Only a semi-quantitative agreement with the experimental data was obtained. However, the differences between pKaapp of a given indicator in two micellar solutions do much better agree with the experimental data. Accordingly, the experimental Ψ values of ionic micelles, as determined using the pKaapp in nonionic micelles as pKai, are reproduced with reasonable accuracy for the corresponding indicator. However, following the experimental data, a scatter of the Ψ values obtained with different indicators for given micelles is observed. This problem may be the subject of further research.

Comparison of adsorption ability of PAM, APAM and CPAM on Sodium-Montmorllonite surface: A molecular dynamics study

Swelling of clay minerals caused by the adsorption of water is one of the main problems encountered in oil well drilling industry during the operations of drilling with water-based fluids. Different types of chemicals can be used as inhibitor to solve the hydration of clay minerals in drilling fluids operations. So, the adsorption process of novel polymer inhibitor remained as well a complex surface phenomenon to understand. Recently, the polymer adhesion mechanism and the development of novel polymer inhibitors that can impart improved adhesion characteristics have become ultimately important to the drilling process. In this research, molecular dynamics simulations are applied to quantify and compare the adsorption density of PAM (Nonionic Polyacrylamide), APAM (Anionic Polyacrylamide) and CPAM (Cationic Polyacrylamide) on Sodium Montmorllonite (Na-MMT) Surface. And also to analyze the hydration inhibition effectiveness for solving shale swelling problem while drilling well. This work mainly explained and summarized the parameters which achieve directly the adsorption mechanism and affect the inhibition process. Including the adsorption characteristics of PAM, APAM and CPAM. The simulation results show that PAM and APAM molecules have low adsorption density on Na-MMT surface compared to CPAM molecules. PAM and APAM molecules interact more through h-bonding with their own molecules leading to a weak interaction with Na-MMT particles. CPAM molecules provide high mobility and have good attraction with Na-MMT particles through electrostatic forces, Van der Waals forces and hydrogen bonding. APAM exhibit high energy, as the distance between its molecules and MMT increase, due to high electrostatic repulsion caused by the negative charge. The adhesion of CPAM molecules affects the inhibition of Na-MMT surface hydration more than PAM and APAM.

Adhesion strength of tetrahydrofuran hydrates is dictated by substrate stiffness

Understanding the hydrate adhesion is important to tackling hydrate accretion in petro-pipelines. Herein, the relationship between the Tetrahydrofuran (THF) hydrate adhesion strength (AS) and surface stiffness on elastic coatings is systemically examined by experimental shear force measurements and theoretical methods. The mechanical factor-elastic modulus of the coatings greatly dictates the hydrate AS, which is explained by the adhesion mechanics theory, beyond the usual factors such as wettability and structural roughness. Moreover, the hydrate AS increases with reducing the thickness of the elastic coatings, resulted from the decrease of the apparent surface elastic modulus. The effect of critical thickness for the elastic materials with variable elastic modulus on the hydrate AS is also revealed. This study provides deep perspectives on the regulation of the hydrate AS by the elastic modulus of elastic materials, which is of significance to design anti-hydrate surfaces for mitigation of hydrate accretion in petro-pipelines.

Nickel chloride removal and insights into heavy metal removal by hydrate-based method

Heavy metal ion in waste water can be potential treated by hydrate formation and dissociation. In this work, nickel chloride was chosen for preparing heavy metal solution, which was then removed by forming methane (CH4) hydrate. Four common factors of stirring speed, hydration time, temperature, and concentration were considered respectively. The nickel chloride removal efficiency reached 71.8% with the dissociated water of 44.9% for the stirring speed, hydration time, temperature, and nickel chloride concentration of 400 r/min, 1 h, 271.1 K, and 100 ppm, respectively. Adhered heavy metal solution on the hydrate surface resulted in the impurity of heavy metal removal by hydrate-based method, and wrapped heavy metal solution by accumulated hydrate was another main reason for the impurity of heavy metal removal. In addition, a flushing water method was proposed and conducted. Nickel chloride removal efficiency was improved to 89.5% with the yield of dissociated water of 44.2%. Finally, controlling hydrate formation conditions and combining hydrate-based method with other method were also proposed to enhance the heavy metal removal efficiency.

Acid Radical Tolerance of Silane Coatings on Calcium Silicate Hydrate Surfaces in Aggressive Environments: The Role of Nitrate/Sulfate Ratio.

Silane is known as an effective coating for enhancing the resistance of concrete to harmful acids and radicals that are usually produced by the metabolism of microorganisms. However, the mechanism of silane protection is still unclear due to its nanoscale attributes. Here, the protective behavior of silane on the calcium silicate hydrate (C-S-H) surface is examined under the attack environment of nitrate/sulfate ions using molecular dynamics simulations. The findings revealed that silane coating improved the resistance of C-S-H to nitrate/sulfate ions. This resistance is considered the origin of silane protection against harmful ion attacks. Further research on the details of molecular structures suggests that the interaction between the oxygen in the silane molecule and the calcium in C-S-H, which can prevent the coordination of sulfate and nitrate to calcium on the C-S-H surface, is the cause of the silane molecules' strong adsorption. These results are also proved in terms of free energy, which found that the adsorption free energy on the C-S-H surface followed the order silane > sulfate > nitrate. This research confirms the excellent protection performance of silane on the nanoscale. The revealed mechanism can be further used to help the development of high-performance composite coatings.

A Soil Hydraulic Conductivity Equation Incorporating Adsorption and Capillarity

A soil’s hydraulic conductivity is a highly nonlinear function of water content, decreasing many orders of magnitude from its saturated state to dry state. This nonlinearity is a macroscopic manifestation of microscopic soil properties of pore structure, pore connectivity, and mineral–water interaction. These microscopic soil properties are underpinned by two distinct soil–water interaction mechanisms: adsorption and capillarity. Herein, a soil hydraulic conductivity equation was developed by incorporating capillary pore flow and adsorptive film flow. The capillary pore flow is captured via a model of bundle of cylindrical capillaries, whereas the adsorptive film flow is established using a film thickness function incorporating adsorption mechanisms of the electric double layer, van der Waals, surface hydration, and cation hydration potentials. The transition between adsorptive film flow and capillary flow is delineated by a water cavitation probability function. The proposed soil hydraulic conductivity equation automatically can fulfill the five necessary physical constraints imposed by underlying soil–water interaction characteristics. The proposed hydraulic conductivity equation can capture the hydraulic conductivity data very well for a wide array of soils, and outperforms several established soil hydraulic models in full matric potential ranges, especially in the low matric potential range in which adsorptive film flow is dominant.

Dynamics of underwater microparticle adhesion to soft hydrated surfaces: Modeling and analysis by time-dependent AFM force spectroscopy

HypothesisUnderstanding the attachment and detachment of microparticles and living cells to surfaces is crucial for developing antifouling strategies. Hydrogel coatings have shown promise in reducing fouling and particle adhesion due to their softness and high water content, yet the mechanisms involved are dynamic and complex, and relevant parameters are not easily accessible. AFM-based force spectroscopy (FS) experiments with colloidal probe particles is a direct way of evaluating adhesive and mechanical relaxational dynamics, yet their interpretation and modeling has been challenging. The present study proposes and examines several dynamic models, suitable for quantitative analysis of FS results with model probe particle on hydrogels surfaces. ExperimentsFS were performed using polyethylene glycol (PEG) hydrogels and polystyrene microspheres including particle attachement to the hydrogel surface (loading), holding the particle on the surface with a constant force for variable times (dwell) and pulling the particle away from the surface (unloading) FindingsIt was found that a viscoelastic extension of the classical JKR model with energy of adhesion unevenly distributed over the contact area and vanishing at its circumferences accurately described all FS experiments and yielded physically consistent viscoelastic and adhesive dynamic parameters, steadily changing with dwell time and applied force. The observed time evolution and force dependence were rationalized as combination of osmotic and osmo-mechnical relaxation in the contact region.

Experimental and computational investigations of the abnormal slow dissociation behavior of CH4 hydrate in the presence of Poly(N-vinylcaprolactam)

In this study, the dissociation behavior of CH4 hydrate in the absence and presence of poly(N-vinylcaprolactam) (PVCap) was closely investigated using a combination of experimental techniques, including in-situ Raman spectroscopy and high-pressure micro-differential scanning calorimetry (HP μ-DSC), and molecular dynamics (MD) simulations. The experimental results clearly demonstrated that CH4 hydrate dissociated more slowly and in two steps in the presence of PVCap. The MD simulations revealed that this slow and two-step dissociation was mainly due to the adsorption of PVCap onto the hydrate surface, which hindered the mass transfer of CH4 from the hydrate into the solution. The high viscosity and steric hindrance of PVCap also impeded the formation and growth of CH4 bubbles during the hydrate dissociation, contributing to the slower dissociation of CH4 hydrate in the PVCap solution. The broad and asymmetric shape of the last endothermic peak observed via HP μ-DSC was caused by the adsorption of PVCap during CH4 hydrate dissociation. The findings of this study provide valuable insights into the precise mechanism of hydrate dissociation in the presence of kinetic hydrate inhibitors.

Water Film-Driven Brucite Nanosheet Growth and Stacking.

Thin water films that form by the adhesion and condensation of air moisture on minerals can initiate phase transformation reactions with broad implications in nature and technology. We here show important effects of water film coverages on reaction rates and products during the transformation of periclase (MgO) nanocubes to brucite [Mg(OH)2] nanosheets. Using vibrational spectroscopy, we found that the first minutes to hours of Mg(OH)2 growth followed first-order kinetics, with rates scaling with water loadings. Growth was tightly linked to periclase surface hydration and to the formation of a brucite precursor solid, akin to poorly stacked/dislocated nanosheets. These nanosheets were the predominant forms of Mg(OH)2 growth in the 2D-like hydration environments of sub-monolayer water films, which formed below ∼50% relative humidity (RH). From molecular simulations, we infer that reactions may have been facilitated near surface defects where sub-monolayer films preferentially accumulated. In contrast, the 3D-like hydration environment of multilayered water films promoted brucite nanoparticle formation by enhancing Mg(OH)2 nanosheet growth and stacking rates and yields. From the structural similarity of periclase and brucite to other metal (hydr)oxide minerals, this concept of contrasting nanosheet growth should even be applicable for explaining water film-driven mineralogical transformations on other related nanominerals.

Surface hydration of zircon and its influence on the adsorption of typical flotation collectors: First-principle calculations

Zirconium and hafnium are critical metals mainly extracted from the zircon mineral. However, due to the unclear surface properties of zircon, most designed flotation collectors (Surfactants to selectively enhance the hydrophobicity of targeted materials) cannot recover zircon effectively. Herein, zircon surface hydration microstructures and their effects on the adsorption of typical flotation collectors (i.e., phosphates, hydroxamic acids, carboxylic acids) have been revealed by systematic first-principles calculations. The speciation diagram and the surface hydration microstructures of zircon have shown that surface Zr sites with small coordination numbers have stronger water affinity. Water molecules have affected the final stable adsorption configurations of the collector. The further obtained adsorption energy of collectors shows that water molecules have weakened the activity of zircon surfaces and reduced the interaction intensity between collectors and surfaces. These results indicate that collectors with stronger negative charges and a lower highest occupied molecular orbital (HOMO) energy can tightly bind with the zircon surface. The electron localization function, density of states, and crystal orbital overlap population have consistently shown that collectors have formed ionic bonds with surface Zr sites. These conclusions should be meaningful for further design of flotation collectors to realize selective zircon flotation.