Pseudo-Second-Order Kinetic Equation for Describing the Effect of Sorbent and Sorbate Concentrations.

The sorbent concentration (Cs) effect and sorbate initial concentration (C0) effect are common phenomena observed in the study of adsorption kinetics at solid-liquid interfaces. That is, adsorption rate constants simulated with classical kinetic equations, such as the pseudo-second-order (PSO) model, for a given system vary with Cs and C0. The classical kinetic equations cannot predict or describe the "Cs-effect" and "C0-effect" (called "C-effects" here). In the current work, the dynamic partition coefficient of sorbate between solid and liquid phases (Kt) was used to describe the adsorption kinetic processes. Based on the surface component activity (SCA) model, which assumes the activity coefficients of the surface components (fs) are not equal to unity but rather a function of Cs and the adsorption capacity (or C0) and referring to the classical PSO model, a new kinetic equation was established, called the "SCA-PSO kinetic model", and its two parameters, the intrinsic equilibrium partition coefficient (Ke0) and the intrinsic rate constant (k20), are independent of Cs and C0. In addition, the new model relates Kt and the rate constant (k2) to Cs and C0 via fs, and can thus describe the C-effects. The fs can be estimated from the change of equilibrium partition coefficient (Ke) with Cs and C0. The new model predicts that with the increase of Cs and C0, Ke decreases while k2 increases. Its rationality was confirmed by the literature-reported adsorption kinetic data of heavy metals on inorganic and biomass sorbents with the C-effects.

Stability and Crystallinity of Sodium Poly(Heptazine Imide) in Photocatalysis.

Poly(heptazine imide) (PHI) salts, as crystalline carbon nitrides, exhibit high photocatalytic activity and are being extensively researched, but its photochemical instability has not drawn researchers' attention yet. Herein, sodium PHI (PHI-Na) ultrathin nanosheets with increased crystallinity, synthesized by enhancing contact of melamine with NaCl functioning as a structure-induction agent and hard template, exhibits improved photocatalytic hydrogen evolution activity, but low photochemical stability, owing to Na+ loss in the photocatalytic process, which, interestingly, can be enhanced by the common ion effect, e.g., addition of NaCl that is also able to remarkably increase the photoactivity with the apparent quantum yield at 420 nm reaching 41.5 %. This work aims at attracting research peers' attention to photochemical instability of PHI salts and provides a way to enhance their crystallinity.

Correlations of Surface Free Energy and Solubility Parameter with Dielectric Constant and Density for Inorganic Solids.

There should be some intrinsic correlations between the surface free energy (γ) and solubility (δ) parameters, called characteristic parameters here, of substances with their basic physical properties such as the relative dielectric constant (εr) and density (ρ), because they are all related to intermolecular interactions. Several correlations have been proposed empirically (or semiempirically) for liquids, but not for solids. It is essential to establish such correlations for solids because the estimation of γ and δ for solids is difficult and/or time-consuming. In the current work, the γ, δ, εr, and ρ data of 34 inorganic solids were chosen, and possible relationships between the characteristic parameters (γ and δ) and the physical quantities (εr and ρ) were explored by a trial-and-error fitting method based on the data of the solids. Six equations relating γ and δ to εr and δ were established. The γ parameters include total (γt), dispersive (γd), and polar (γp) ones, and the δ parameters include the Hildebrand parameter (δt) and the Hansen-dispersive (δd), polar (δp), and hydrogen-bonding (δh) ones. The empirical equations can be used to estimate the characteristic parameters of inorganic solids from their easily measurable physical quantities.

Preparation of hydrogels based on poplar cellulose and their removal efficiency of Cd(II) from aqueous solutions.

Industrial heavy metal-contaminated wastewater is one of the main water pollution problems. Adsorbents are a promising method for the removal of heavy metal contaminants. Herein, polyaspartic acid/carboxymethyl poplar sawdust hydrogels (PASP/CMPP) and ascorbic acid/carboxymethyl poplar sawdust hydrogels (VC/CMPP) were prepared by aqueous polymerization using alkalized poplar sawdust (CMPP) as the substrate and PASP and vitamin C (VC) as modifiers. The effective results, provided by the characterization analysis of SEM and BET, indicate that the surface of the PASP/CMPP hydrogel has a larger number of loose pores and a larger pore volume than the VC/CMPP hydrogel. The treatment effects of the two hydrogels on simulated wastewater containing Cd(II) were investigated by a batch of experiments. The results showed that PASP/CMPP had a better adsorption effect than VC/CMPP under the same adsorption conditions. Interestingly, the solid concentration effect was found in the process of sorption kinetics and sorption isotherms. The sorption kinetic curves of Cd(II) on PASP/CMPP were well-fitted by the quasi-second-order kinetics under different adsorbent concentrations. The adsorption conforms to Langmuir and Freundlich adsorption isotherm models. More importantly, PASP/CMPP composites are expected to be used as a new kind of environmental adsorbent for wastewater treatment.

Interfacial Affinity Determined Photocatalytic Activity: A Comparison between Defective and Bulk Polymeric Carbon Nitride.

The photoexcited charge separation efficiency of photocatalysts is generally considered as the key factor for enhancement of their photocatalytic activity, and sometimes, their photoabsorption capability and interfacial reaction kinetics play a key part, but the role of interfacial affinity of photocatalysts with substrates was rarely researched systematically. Herein, nitrogen vacancy-modified polymeric carbon nitride porous nanotubes (PCNpts) were simply synthesized, using tartaric acid as a crosslinking and corrosion agent, and exhibit a remarkable increment in surface area, wettability, photoabsorption and charge separation capability, and photocatalytic activity in water splitting to produce H2, but, interestingly, exhibit substrate-dependent variation of photoactivity in contaminant degradation, compared with bulk PCN. More interestingly, the interfacial affinity of PCNpts and PCN with contaminants and H2O, rather than photoabsorption and charge separation capability, is confirmed to dominate their photoactivity.

General Adsorption Model to Describe Sigmoidal Surface Tension Isotherms of Binary Liquid Mixtures.

Surface tension (σ) isotherms of liquid mixtures can be divided into Langmuir-type (L-type, including LI- and LII-type) and sigmoid-type (S-type, including SI- and SII-type). Many models have been developed to describe the σ-isotherms. However, the existing models can well describe the L-type isotherms, but not the S-type ones. In the current work, a thermodynamic model, called the general adsorption model, was developed based on the assumption of surface aggregation occurring in the surface layers, to relate the surface composition with the bulk one. By coupling the general adsorption model with the modified Eberhart model, a two-parameter equation was developed to relate the σ with the bulk composition. Its rationality was examined using the σ data of 10 binary mixtures. The results indicate that the new model can accurately describe the S- and L-type isotherms of binary liquid mixtures, showing a good universality. One advantage of the model is that its two parameters, i.e., the adsorption equilibrium constant (K) and the average aggregation number (n), can be estimated by linear fitting experimental σ data, thereby obtaining unique values. This model suggests that the S- and LII-type isotherms arise from the surface aggregation (n ≠ 1). In addition, the standard molar Gibbs free energy of surface adsorption (ΔG̃ad0) and the apparent surface layer thickness (τ) were analyzed for 10 binary mixtures. The ΔG̃ad0 data suggest that the order of adsorption tendency is LI-type ≫ SI-type ≈ SII-type > LII-type, and the strong adsorption usually corresponds to large τ. This work provides a feasible model for describing the S-type isotherms and a better understanding of the surface properties of liquid mixtures.

MnOx Film-Coated NiFe-LDH Nanosheets on Ni Foam as Selective Oxygen Evolution Electrocatalysts for Alkaline Seawater Oxidation.

Compared to freshwater electrolysis, seawater electrolysis to produce hydrogen is preferable and more promising, but this technology is plagued by the electrode's corrosion and oxidative reactions of the competitive Cl- ion on the anode. To develop efficient oxygen evolution reaction (OER) catalysts for seawater electrolysis, the ultrathin MnOx film-covered NiFe-layered double-hydroxide nanosheet array is directly assembled on Ni foam (MnOx/NiFe-LDH/NF) by hydrothermal and electrodeposition in turn. This catalyst demonstrates excellent OER-selective activity in alkaline saline electrolytes. In 1 M KOH/0.5 M NaCl and 1 M KOH/seawater electrolytes, MnOx/NiFe-LDH/NF exhibits lower overpotentials at 100 mA cm-2 (η100 values of 265 and 276 mV, respectively) and Tafel slopes (73 and 77 mV decade-1, respectively) than does the NiFe-LDH/NF electrode (η100 values of 298 and 327 mV and Tafel slopes of 91 and 140 mV decade-1, respectively). In alkaline saline solutions, the stability and durability of the former are also better than those of the latter. The good OER selectivity and catalytic performance are attributed to the MnOx overlayer that selectively blocks Cl- anions from approaching catalytic centers, and the good conductivity, fast kinetics, more oxygen vacancies, and abundant active sites of MnOx/NiFe-LDH/NF. The robust stability is due to the enhanced resistance for Cl- corrosion stemming from the MnOx protective film. Hence, MnOx/NiFe-LDH/NF can act as a promising OER electrocatalyst for alkalized natural seawater electrolysis.

Ion-Induced Synthesis of Crystalline Carbon Nitride Ultrathin Nanosheets from Mesoporous Melon for Efficient Photocatalytic Hydrogen Evolution with Synchronous Highly Selective Oxidation of Benzyl Alcohol.

Crystalline carbon nitride (CCN) with a poly(heptazine imide) structure is efficient in photocatalytic hydrogen evolution (PHE), but synthesis of CCN ultrathin nanosheets (CCNuns) and their use in PHE with selective organic oxidation are still rare. Herein, CCNuns with Na+ doping are prepared using NaCl as the ion-induction and templating agent and mesoporous melon as the feedstock, exhibiting efficient synchronous PHE and benzyl alcohol oxidation to benzaldehyde, with an apparent quantum yield of 10.5% at 420 nm and a visible light PHE rate that is 94.3 times that of bulk polymeric carbon nitride (PCN). The selectivity of benzaldehyde formation (90.5%) is also much higher than that of PCN (40.7%). Interestingly, this selectivity increases gradually with increasing light wavelengths. The high photoactivity of CCNuns originates from their ultrathinness and Na+ doping, which considerably enhance the photogenerated charge separation. This work opens up an avenue for the synthesis of CCNuns and extends their application.

PEO-PPO-PEO induced holey NiFe-LDH nanosheets on Ni foam for efficient overall water-splitting and urea electrolysis.

Exploring the transition-metal-based bifunctional electrocatalysts with high performance for efficient water-splitting and urea electrolysis is significant but challenging. This work presents the in situ preparation of holey NiFe-LDH nanosheets on Ni foam (H-NiFe-LDH/NF) via a one-step hydrothermal method in the presence of PEO-PPO-PEO as the soft template. The holey NiFe-LDH nanosheets provide a high electrochemical surface area, more edge catalytic sites, and abundant oxygen vacancies. Consequently, H-NiFe-LDH/NF exhibits excellent catalytic activity to oxygen evolution, urea oxidation, and hydrogen evolution reactions (OER, UOR, and HER) with good stability in alkaline electrolytes. This electrode requires an overpotential of 261 mV for the OER, a potential of 1.480 V for the UOR to achieve a current density of 100 mA cm-2 in alkaline solutions. By employing the self-supported electrode as both the anode and cathode, this electrolysis cell (H-NiFe-LDH/NF||H-NiFe-LDH/NF) gains current densities of 10 and 100 mA cm-2 at low cell voltages of 1.575 and 1.933 V in the 1.0 M KOH solution. After adding 0.33 M urea, the voltages to deliver 10 and 100 mA cm-2 respectively decrease to 1.418 and 1.691 V. The H-NiFe-LDH/NF electrode also shows excellent stability for water-splitting and urea electrolysis. This work not only contributes to developing a low-cost, high-efficiency, bifunctional electrocatalyst but also provides a practically feasible approach for urea-rich wastewater electrolysis.

Adsorption of Cetylpyridinium Chloride at Silica Nanoparticle/Water Interfaces (II): Dependence of Surface Aggregation on Particle Size.

Herein, we report a thermodynamic model that relates the adsorption (aggregation) parameters of surfactants at solid/liquid interfaces to particle radius (r). The adsorption (aggregation) parameters include adsorption amounts, equilibrium constants (or the standard Gibbs free energy changes), the critical surface micelle concentration (csmc), and the average aggregation number of surface micelles (n). The model predicts the size dependence of the surface aggregation of surfactants, which is determined by the changes in the interfacial tension and the molar volume of surface components caused by adsorption. In addition, the adsorption of cetylpyridinium chloride (CPyCl), a cationic surfactant, on silica nanoparticles with different r values (ca. 6-61 nm) was determined at 298 K and pH 4, showing an obvious size dependence, consistent with the prediction of the model. With an increase in r, the adsorption isotherm changes from the double-plateau type to the Langmuir type, accompanied by obvious changes in the adsorption parameters. The size-dependent adsorption data can be well described using the model equations, indicating that the model presented here is acceptable. In addition, the model can extract information on the interfacial tensions from adsorption data. We think that the model deepens the understanding of the aggregation phenomena of surfactants at solid/liquid interfaces.

Vesicle formation of single-tailed amphiphilic alkyltrimethylammonium bromides in water induced by dehydration-rehydration.

We recently found that rough glass surfaces (RGSs) can in situ mediate the micelle-to-vesicle transition in single-component solutions of simple single-tailed amphiphiles (STAs), but only result in a relatively small number of vesicles coexisting with a large number of micelles. In the current work, a dehydration-rehydration (DHRH) method was used to induce the formation of vesicles in the single-component aqueous solutions of alkyltrimethylammonium bromides (CnTABs, n = 12, 14, and 16), a kind of typical cationic STAs. That is, a CnTAB micelle solution dropped on smooth glass surfaces (SGSs) was first dried, and the dried CnTAB aggregates were then rehydrated in a monomer solution of CnTAB. A large population of vesicles and even pure vesicle (or vesicle-dominated) systems were obtained, indicating that the DHRH process could more effectively induce the formation of STA vesicles than RGS in situ mediation. The so-obtained vesicles were characterized using DLS, FF-/cryo-TEM, AFM, SAXS, and fluorescence techniques, and their stability was determined. In addition, the effects of the conditions of DHRH and the chain length of CnTABs on the vesicle formation were examined. It was demonstrated that the vesicles can be formed as long as the concentrations of CnTABs in the rehydrated systems are higher than their critical micelle concentrations. The size and wall thickness of vesicles increase with an increase in chain length. A possible mechanism for the DHRH-induced vesicle formation is proposed: bilayer sheets are formed on SGSs during dehydration, and then detached from the SGSs to form vesicles during rehydration. A highly interdigitated structure of alkyl chains between two leaflets was identified in the bilayers, which probably is the origin of the formation and stability of STA vesicles.

Single-atom cobalt-hydroxyl modification of polymeric carbon nitride for highly enhanced photocatalytic water oxidation: ball milling increased single atom loading.

Expediting the oxygen evolution reaction (OER) is the key to achieving efficient photocatalytic overall water splitting. Herein, single-atom Co-OH modified polymeric carbon nitride (Co-PCN) was synthesized with single-atom loading increased by ∼37 times with the assistance of ball milling that formed ultrathin nanosheets. The single-atom Co-N4OH structure was confirmed experimentally and theoretically and was verified to enhance optical absorption and charge separation and work as the active site for the OER. Co-PCN exhibits the highest OER rate of 37.3 µmol h-1 under visible light irradiation, ∼28-fold higher than that of common PCN/CoO x , with the highest apparent quantum yields reaching 4.69, 2.06, and 0.46% at 400, 420, and 500 nm, respectively, and is among the best OER photocatalysts reported so far. This work provides an effective way to synthesize efficient OER photocatalysts.

A Model for the Structure of Adsorbed Layers at Solid/Liquid Interfaces.

Understanding the structure of adsorbed layers, including their composition (the mole fraction of sorbate, xA) and thickness (dal), is of great significance for revealing the nature of adsorption and guiding its applications. Many techniques have been used to estimate the structure of adsorbed layers of organics at solid/liquid interfaces. However, there is still a lack of feasible thermodynamic models to describe the correlation between the structure (more precisely, xA and dal) and the equilibrium adsorption amount (Γe). Herein, a thermodynamic model, called the dynamic bonding equilibrium (DBE) model, was developed on the basis of the adsorption equilibrium thermodynamics with an assumption that, at adsorption equilibrium, the sorbate and solvent within the adsorbed layer both exist in different bonding states. The DBE model relates xA and dal with Γe and thus can predict or describe the structure (xA and dal) of adsorbed layers from Γe. Its rationale was confirmed by the literature-reported adsorption data of organics, including surfactants, proteins, and polymers, on hydrophilic and hydrophobic surfaces in water. This work provides a feasible approach for obtaining information about the structure of adsorbed layers at solid/liquid interfaces.

Electrodeposition of NiFe-layered double hydroxide layer on sulfur-modified nickel molybdate nanorods for highly efficient seawater splitting.

Developing high-efficiency and earth-abundant electrocatalysts for electrochemical seawater-splitting is of great significance but remains a grand challenge due to the presence of high-concentration chloride. This work presents the synthesis of a three-dimensional core-shell nanostructure with an amorphous and crystalline NiFe-layered double hydroxide (NiFe-LDH) layer on sulfur-modified nickel molybdate nanorods supported by porous Ni foam (S-NiMoO4@NiFe-LDH/NF) through hydrothermal and electrodeposition. Benefiting from high intrinsic activity, plentiful active sites, and accelerated electron transfer, S-NiMoO4@NiFe-LDH/NF displays an outstanding bifunctional catalytic activity toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in both simulated alkaline seawater and natural seawater electrolytes. To reach a current density of 100 mA cm-2, this catalyst only requires overpotentials of 273 and 315 mV for OER and 170 and 220 mV for HER in 1 M KOH + 0.5 M NaCl freshwater and 1 M KOH + seawater electrolytes, respectively. Using S-NiMoO4@NiFe-LDH as both anode and cathode, the electrolyzer shows superb overall seawater-splitting activity, and respectively needs low voltages of 1.68 and 1.73 V to achieve a current density of 100 mA cm-2 in simulated alkaline seawater and alkaline natural seawater electrolytes with good Cl- resistance and satisfactory durability. The electrolyzer outperforms the benchmark IrO2||Pt/C pair and many other reported bifunctional catalysts and exhibits great potential for realistic seawater electrolysis.

Adsorption of Cetylpyridinium Chloride at Silica Nanoparticle/Water Interfaces (I): Dependence of Adsorption Equilibrium on Particle Size.

In the current work, a size-effect model was developed to describe the particle size-dependence of adsorption at solid/liquid interfaces. A parameter, ΔQad, was introduced, defined as the change of the product of the solid/liquid interfacial tension and the molar volume of solid surface components caused by adsorption. The model predicts that with a decrease in particle radius (r), the saturation adsorption amount per unit area (Γm, mol/m2) decreases, while the change of the adsorption equilibrium constant (Kad) is determined by the ΔQad, namely, it decreases if ΔQad > 0 but increases if ΔQad < 0. There exists a critical r at which the saturation adsorption amount per unit mass (Γmg, mol/g) attains a maximum. In addition, the adsorption of cetylpyridinium chloride (CPyCl), a cationic surfactant, on silica nanoparticles with different r (ca. 6-61 nm) values was determined at 298 K and pH 9, showing an obvious size-dependence. With a decrease in r, Kad and Γm decrease, indicating a decrease in the affinity of silica particles toward CPyCl. The size-dependent adsorption data can be well described using our model. Adsorption can affect the molar volume of the solid surface phase, which plays an important role in the size-dependence of adsorption. This work provides a better understanding of the size-dependent adsorption phenomenon at solid/liquid interfaces.

Spontaneous vesicle formation and vesicle-to-α-gel transition in aqueous mixtures of sodium monododecylphosphate and guanidinium salts.

Monoalkyl phosphates (MAPs) are one kind of important single-chain weak acid/salt type surfactants, but the understanding of their aggregation behavior in water is very limited due to their insolubility at room temperature. In the current work, the effect of guanidinium salts (GuSalts) on the solubility of sodium monododecylphosphate (SDP), a typical MAP, in water was determined at 25.0 °C, and the aggregation behavior of SDP in the GuSalt/water mixtures was investigated. The solubility of SDP is significantly improved by GuSalts including GuCl, GuSO4, GuSO3, GuPO4, and GuCO3 at 25.0 °C, resulting in an isotropic phase. SDP vesicles are spontaneously formed in the isotropic phase, with a critical vesicle concentration of ∼1.0 mM independent of the type of GuSalts. A "bridging dimer" mechanism is proposed to explain the formation of SDP vesicles. The SDP vesicles have a unilamellar structure with a size of ∼80 nm and an alkyl interdigitated degree of ∼25%, and exhibit size-selective permeability. Interestingly, a temperature-induced reversible transition between vesicles and α-gels was observed for the SDP/GuSalt/H2O systems when the SDP content is higher than 20 mM. The α-gels obtained are composed of vesicles and bilayer sheets, showing similar viscoelasticity to conventional gels, although their water content is as high as ∼98 wt%. The microviscosity of SDP vesicle membranes (ca. 35.79-49.34 mPa s at 25.0 °C) and the transition temperature between vesicles and α-gels (ca. 21.0-22.8 °C) are all dependent of the type of GuSalts. This work deepens the understanding of the aggregation behavior of MAPs and also provides valuable information for their practical applications.

Vesicle formation of single-chain amphiphilic 4-dodecylbenzene sulfonic acid in water and micelle-to-vesicle transition induced by wet-dry cycles.

Simple single-chain amphiphiles (SCAs) can form vesicular structures in their single-component aqueous solutions, which has attracted great attention, but the understanding of their aggregation behavior is still limited. In this work, the aggregation behavior of 4-dodecylbenzene sulfonic acid (DBSA), a typical simple SCA, in water was investigated. The structure and properties of the aggregates formed were determined. In particular, the effect of wet-dry cycles on the structures of aggregates was examined. The mechanisms of aggregate formation and structural transition were discussed. It was found that the increase of DBSA concentration can drive the occurrence of a micelle-to-vesicle transition, showing a critical micelle concentration and critical vesicle concentration of ∼0.53 and 2.14 mM, respectively. The vesicles formed coexist with micelles in solution, with a unilamellar structure and ∼80 nm size, and exhibit size-selective permeability. In addition, the vesicles show remarkable stability upon long-term storage, exposure to high temperature, and freeze-thaw cycles. The H-bonding interaction between DBSA species and the interdigitated structure of alkyl chains in bilayers play a key role in the formation and stability of DBSA vesicles. Interestingly, it was found that the wet-dry cycle can induce a micelle-to-vesicle transition and an obvious increase in the size of the original vesicles, accompanied by the formation of some multilamellar vesicles. This work provides a better understanding of the aggregation behavior of simple SCAs in their single-component aqueous solutions.

An aqueous two-phase system formed in single-component solution of α-ketooctanoic acid.

Aqueous two-phase systems (ATPSs), consisting of two immiscible water-rich phases, have received great attention. So far, all of ATPSs reported are formed by two water-soluble compounds in aqueous media. Herein, we report an ATPS formed in the single-component aqueous solution of α-ketooctanoic acid (KOCOOH), a weakly acidic surfactant, without any additives. Its formation originates from the coexistence of micelles and vesicles in the system, the former existing in the upper phase and the latter in the lower phase. The phase behavior and microstructures of KOCOOH in aqueous solution were determined. A concentration-driven stepwise aggregation was identified for the KOCOOH solution. With an increase in the KOCOOH concentration, vesicles, oil droplets, micelles, strip bilayers, and planar lamellar phase form successively; macroscopically, the system exhibits a homogeneous transparent single-phase, turbid dispersion, two phases, a bluish single-phase, and a colorless transparent single-phase in turn. The constantly changing ionization state of KOCOOH in aqueous solution plays an important role in the phase and aggregate structure transition. This work deepens the understanding of ATPSs, and the ATPS formed by KOCOOH may have potential applications such as in the separation and purification of biomolecules and the construction of hierarchical protocell models.

Solvothermal synthesis of carbonate-type layered double hydroxide monolayer nanosheets: Solvent selection based on characteristic parameter matching criterion.

Monolayer nanosheets of CO32--type layered double hydroxides (LDHs) have many special applications, but their fabrication is challenging. Herein, Co2Al-CO3 and Co2Fe-CO3 LDH nanosheets were synthesized via a solvothermal method. 31 solvents with different characteristic parameters, including the surface free energy (γ) and solubility (δ) parameters were chosen, to explore the correlation between the formation of monolayer LDHs (ML-LDHs) and the characteristic parameters of solvents. The results reveal that when the solvents used have the characteristic parameters matching to those of the LDHs, CO32--type ML-LDHs with a thickness of ca. 1 nm can be obtained. The mixed-solvent strategy can provide the effective solvents for the synthesis of ML-LDHs. The dispersions of CO32--type ML-LDHs can be stable for at least six months without obvious precipitation. In addition, it is demonstrated that the δ parameters of LDHs can be calculated from the γ parameters via the molar volume-free γ-δ equations developed previously. Furthermore, a new parameter called "surface free energy distance" is introduced, which can be used for screening effective solvents for the synthesis of ML-LDHs. To the best of our knowledge, this is the first time to investigate the applicable of the characteristic parameter matching principle for the bottom-up synthesis of ML-LDHs. This work deepens the understanding on the feature of CO32--type LDHs and provides a solvent selection strategy for the synthesis of CO32--type ML-LDHs.

The pivotal role of defects in fabrication of polymeric carbon nitride homojunctions with enhanced photocatalytic hydrogen evolution.

Fabrication of homojunctions is a cost-effective efficient way to enhance the photocatalytic performance of polymeric carbon nitride (CN), but the generation of defects upon synthesizing CN homojunctions and their roles in the homojunction fabrication were hardly reported. Herein, nitrogen-deficient CN homojunctions were simply synthesized by calcining dicyandiamide-loaded CN (prepared from urea and denoted as UCN) with dicyandiamide polymerizing into CN (denoted as DCN) and simultaneous formation of nitrogen vacancies in the surface of UCN. Fabrication of the nitrogen-deficient UCN (dUCN)/DCN homojunction depends on the nitrogen vacancy content in dUCN which can tune the energy band structure of dUCN from not matching to matching with that of DCN. The dUCN/DCN homojunction exhibits extended optical absorption and remarkably enhanced charge separation and photocatalytic H2 evolution, compared with UCN and DCN. This work illustrates the pivotal role of defects in fabricating CN homojunctions and supplies a new facile way to synthesize nitrogen-deficient CN.