Hard Soft Acid Base Theory Research Articles

Delocalization State-Stabilized Znδ+ Active Sites for Highly Selective and Durable CO2 Electroreduction.

Zinc (Zn)-based materials are cost-effective and promising single-metal catalysts for CO2 electroreduction to CO but is still challenged by low selectivity and long-term stability. Undercoordinated Zn (Znδ+) sites have been demonstrated to be powerful active centers with appropriate *COOH affinity for efficient CO production However, electrochemical reduction conditions generally cause the inevitable reduction of Znδ+, resulting in the decline of CO efficiency over prolonged operation. Herein, a Zn cyanamide (ZnNCN) catalyst is constructed for highly selective and durable CO2 electroreduction, wherein the delocalized Zn d-electrons and resonant structure of cyanamide ligand prevent the self-reduction of ZnNCN and maintain Znδ+ sites under cathodic conditions. The mechanism studies based on density functional theory and operando spectroscopies indicate that delocalized Znδ+ site can stabilize the key *COOH intermediate through hard-soft acid-base theory, therefore thermodynamically promoting CO2-to-CO conversion. Consequently, ZnNCN delivers a CO Faradaic efficiency (FE) of up to 93.9% and further exhibits a remarkable stability lifespan of 96h, representing a significant advancement in developing robust Zn-based electrocatalysts. Beyond expanding the variety of CO2 reduction catalysts, this work also offers insights into understanding the structure-function sensitivity and controlling dynamic active sites.

Facile preparation of NiFe2O4 decorated chitosan-graphene oxide for efficient remediation of Co(II) and adsorption mechanism

In the background of severe water pollution, adsorption is a charming technique for heavy metal remediation. In this work, NiFe2O4 decorated chitosan-graphene oxide (NFCG) was prepared by simple hydrothermal method for Co(II) remediation application. Adsorption mechanism was elaborately elucidated based on multiple evidences extracted from adsorption fitting (isotherms, thermodynamics and kinetics), spectroscopic test (XPS, UV–Vis absorption, fluorescent emission and Raman spectra) and the hard-soft acid-base (HSAB) theory inspection. Result shows, for Co(II) with initial concentration 200 mg·L−1, NFCG with dosage 500 mg·L−1 reaches adsorption equilibrium in 24 min, rendering removal percentage and adsorption amount 96.87 % and 387.48 mg·g−1, respectively. Owing to the efficient recovery enabled by paramagnetism, NFCG keeps adsorption amount 311.01 mg·g−1 for Co(II) after six consecutive cycles. Moreover, NFCG exhibits selectivity towards Co(II) under the coexistence of common interfering substances. Adsorption fitting suggests chemical adsorption based on heterogeneous affinity. Spectroscopic analysis discloses, CO, CO, -C(=O)NH-, OH and aromatic part contribute to Co(II) adsorption via electron donation, forming CoO bond. This atomic scale adsorption mechanism was substantiated by HSAB theory calculation. In brief, this work provides basic knowledge and technical support for fabricating high efficiency magnetic bio adsorbent.

AI-assisted models to predict chemotherapy drugs modified with C60 fullerene derivatives.

Employing quantitative structure-activity relationship (QSAR)/ quantitative structure-property relationship (QSPR) models, this study explores the application of fullerene derivatives as nanocarriers for breast cancer chemotherapy drugs. Isolated drugs and two drug-fullerene complexes (i.e., drug-pristine C60 fullerene and drug-carboxyfullerene C60-COOH) were investigated with the protein CXCR7 as the molecular docking target. The research involved over 30 drugs and employed Pearson's hard-soft acid-base theory and common QSAR/QSPR descriptors to build predictive models for the docking scores. Energetic descriptors were computed using quantum chemistry at the density functional-based tight binding DFTB3 level. The results indicate that drug-fullerene complexes interact more with CXCR7 than isolated drugs. Specific binding sites were identified, with varying locations for each drug complex. Predictive models, developed using multiple linear regression and IBM Watson artificial intelligence (AI), achieved mean absolute percentage errors below 12%, driven by AI-identified key variables. The predictive models included mainly quantitative descriptors collected from datasets as well as computed ones. In addition, a water-soluble fullerene was used to compare results obtained by DFTB3 with a conventional density functional theory approach. These findings promise to enhance breast cancer chemotherapy by leveraging fullerene-based drug nanocarriers.

Water-Soluble Lead Sulfide Nanoparticles: Direct Synthesis and Ligand Exchange Routes.

Colloidal semiconductor nanoparticles (NPs) represent an emergent state of matter with unique properties, bridging bulk materials and molecular structures. Their distinct physical attributes, such as bandgap and photoluminescence, are intricately tied to their size and morphology. Ligand passivation plays a crucial role in shaping NPs and determining their physical properties. Ligand exchange (LE) offers a versatile approach to tailoring NP properties, often guided by Pearson's Hard-Soft Acid-Base theory. Lead sulfide (PbS), a semiconductor of considerable interest, exhibits size-dependent tunable bandgaps from the infrared to the visible range. Here, we present two methods for synthesizing water-soluble, polyvinylpyrrolidone (PVP)-coated PbS NPs. The first involves direct synthesis in an aqueous solution while utilizing PVP as the surfactant for the formation of nano-cubes with a crystal coherence length of ~30 nm, while the second involves LE from octadecylamine-coated PbS truncated nano-cubes to PVP-coated PbS NPs with a crystal coherence length of ~15 nm. Multiple characterization techniques, including X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermal gravimetric analysis, confirmed the results of the synthesis and allowed us to monitor the ligand exchange process. Our findings demonstrate efficient and environmentally friendly approaches for synthesizing PVP-coated PbS NPs.

Selective Adsorption of Hazardous Substances from Wastewater by Hierarchical Oxide Composites: A Review.

Large volumes of wastewater containing toxic contaminants (e.g., heavy metal ions, organic dyes, etc.) are produced from industrial processes including electroplating, mining, petroleum exploitation, metal smelting, etc., and proper treatment prior to their discharge is mandatory in order to alleviate the impacts on aquatic ecosystems. Adsorption is one of the most effective and practical methods for removing toxic substances from wastewater due to its simplicity, flexibility, and economics. Recently, hierarchical oxide composites with diverse morphologies at the micro/nanometer scale, and the combination advantages of oxides and composite components have been received wide concern in the field of adsorption due to their multi-level structures, easy functionalization characteristic resulting in their large transport passages, high surface areas, full exposure of active sites, and good stability. This review summarizes the recent progress on their typical preparation methods, mainly including the hydrothermal/solvothermal method, coprecipitation method, template method, polymerization method, etc., in the field of selective adsorption and competitive adsorption of hazardous substances from wastewater. Their formation processes and different selective adsorption mechanisms, mainly including molecular/ion imprinting technology, surface charge effect, hard-soft acid-base theory, synergistic effect, and special functionalization, were critically reviewed. The key to hierarchical oxide composites research in the future is the development of facile, repeatable, efficient, and scale preparation methods and their dynamic adsorption with excellent cyclic regeneration adsorption performance instead of static adsorption for actual wastewater. This review is beneficial to broaden a new horizon for rational design and preparation of hierarchical oxide materials with selective adsorption of hazardous substances for wastewater treatment.

Building a High-Potential Silver-Sulfur Redox Reaction Based on the Hard-Soft Acid-Base Theory.

Sulfur holds immense promise for battery applications owing to its abundant availability, low cost, and high capacity. Currently, sulfur is commonly combined with alkali or alkaline earth metals in metal-sulfur batteries. However, these batteries universally face challenges in cycling stability due to the inevitable issue of polysulfide dissolution and shuttling. Additionally, the inferior stability of metal sulfide discharge compounds results in low S0/S2- redox potentials (<-0.41 V vs SHE). Herein, we leverage the principle of the hard-soft acid-base theory to introduce a novel silver-sulfur (Ag-S) battery system, which operates on the reaction between the soft acid of Ag+ and the soft base of S2-. Due to their high reaction affinity, the discharge compound of silver sulfide (Ag2S) is intrinsically insoluble and fundamentally stable. This not only resolves the polysulfide dissolution issue but also leads to a predominantly high S0/S2- redox potential (+1.0 V vs. SHE). We thus exploit the Ag-S reaction for a primary zinc battery application, which exhibits a high capacity of ∼620 mAh g-1 and a high voltage of ∼1.45 V. This work offers valuable insights into the application of classic chemistry theories in the development of innovative energy storage devices.

Switching CO2 Electroreduction toward Ethanol by Delocalization State-Tuned Bond Cleavage.

The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due to the unfavored formation of oxygenate intermediates on the catalyst surface, the selectivity of C2+ alcohols like ethanol remains unsatisfactory compared to that of ethylene. The bifurcation point (i.e., the CH2═CHO* intermediate adsorbed on Cu via a Cu-O-C linkage) is critical to the C2+ product selectivity, whereas the subsequent cleavage of the Cu-O or the O-C bond determines the ethanol or ethylene pathway. Inspired by the hard-soft acid-base theory, in this work, we demonstrate an electron delocalization tuning strategy of the Cu catalyst by a nitrene surface functionalization approach, which allows weakening and cleaving of the Cu-O bond of the adsorbed CH2═CHO*, as well as accelerating hydrogenation of the C═C bond along the ethanol pathway. As a result, the nitrene-functionalized Cu catalyst exhibited a much-enhanced ethanol Faradaic efficiency of 45% with a peak partial current density of 406 mA·cm-2, substantially exceeding that of unmodified Cu or amide-functionalized Cu. When assembled in a membrane electrode assembly electrolyzer, the catalyst presented a stable CO2-to-ethanol conversion for >300 h at an industrial current density of 400 mA·cm-2.

Probing the Structural Degradation of CsPbBr3 Perovskite Nanocrystals in the Presence of H2O and H2S: How Weak Interactions and HSAB Matter.

Structural degradation of all inorganic CsPbBr3 in the presence of moisture is considered as one of its major limitations to use as an active component in various light-harvesting and light-emitting devices. Herein, we used two similar molecules, H2O and H2S, with similar structures, to follow the decomposition mechanism of CsPbBr3 perovskite nanocrystals. Interestingly, H2O acts as a catalyst for the decomposition of CsPbBr3, which is in contrast to H2S. Our experimental observations followed by density functional theory (DFT) calculations showed that the water molecule is intercalated in the CsPbBr3 perovskite whereas H2S is adsorbed in the (100) planes of CsPbBr3 by a weak electrostatic interaction. According to Pearson's hard-soft acid-base theory, both cations present in CsPbBr3 prefer soft/intermediate bases. In the case of the water molecule, it lacks a soft base and thus it is not directly involved in the reaction whereas H2S can provide a soft base and thus it gets involved in the reaction. Understanding the mechanistic aspects of decomposition can give different methodologies for preventing such unwanted reactions.

Structure of phytic acid functionalized graphene oxide prepared by hydrothermal method based on aqueous species distribution and the hard-soft acid-base theory

Phytic acid functionalized graphene oxide (PA-GO) has encouraging application in environmental treatment. Herein, structure of PA-GO fabricated by hydrothermal method was inspected. Firstly, the aqueous species distribution and ionization states of phytic acid (PA) and graphene oxide (GO) under varying pH was analyzed according to equilibrium thermodynamics to clarify the primary interacting species involved in PA-GO fabrication. Secondly, the hard-soft acid-base (HSAB) theory and spectroscopic characterizations (XPS, FTIR, Raman, UV–Vis and fluorescent spectra) were employed to elucidate the plausible interactions existing in PA-GO. Thermodynamic deduction indicates, C6H6O24P612- is the dominant species of PA, while –OH and –COO- are the dominant state of graphene oxide groups in PA-GO fabrication system. HSAB theory illuminates, the primary interactions occurs between deprotonated oxygen O(O-) and bridged oxygen O(-O-) of phytic acid with hydroxyl group O(Ar-OH) and π electron of graphene oxide. Moreover, electron flows from GO towards PA to induce energy lowering whereby PA-GO is stabilized. HSAB theory prediction was substantiated by spectroscopic analyses. Furthermore, PA-GO efficiently removes ionic dyes in five consecutive cycles with high adsorption capacity. This work may shed light on the fabrication chemistry of PA-GO framework serving as a potential adsorbent.

Stepwise and Controllable Synthesis of Mesoporous Heterotrimetallic Catalysts Based on Predesigned Al4 Ln4 Metallocycles.

The motivation for making heterometallic compounds stemmed from their emergent synergistic properties and enhanced capabilities for applications. However, the atomically precisely controlled synthesis of heterometallic compounds remains a daunting challenge of the complications that arise when applying several metals and linkers. Herein, a stepwise and controlled method is reported for the accurate addition of second and third metals to homometallic aluminum macrocycles based on the synergistic coordination and hard-soft acid-base theory. These heterometallic compounds showed a good Lewis acid catalytic effect, and the addition of hetero-metals significantly improved the catalytic effect and rate, among that the conversion rate of compound AlOC-133 reached 99.9% within half an hour. This method combines both the independent controllability of stepwise assembly with the universality of one-step methods. Based on the large family of clusters, the establishment of this method paves the way for the controllable and customized molecular-level synthesis of heterometallic materials and creates materials customized for preferential application.

Three Robust Isoreticular Metal-Organic Frameworks with High-Performance Selective CO2 Capture and Separation.

Based on the hard-soft acid base (HSAB) theory, three robust isoreticular metal-organic frameworks (MOFs) with nia topology were successfully synthesized by solvothermal reaction {[In3O(BHB)(H2O)3]NO3·3DMA (JLU-MOF110(In)), [Fe3O(BHB)(H2O)3]NO3 (JLU-MOF110(Fe)), and [Fe2NiO(BHB)(H2O)3] (JLU-MOF110(FeNi)) (DMA = N,N-dimethylacetamide, H6BHB = 4,4″-benzene-1,3,5-triyl-hexabenzoic acid)}. Both JLU-MOF110(In) and JLU-MOF110(Fe) are cationic frameworks, and their BET surface areas are 301 and 446 m2/g, respectively. By modification of the components of metal clusters, JLU-MOF110(FeNi) features a neutral framework, and the BET surface area is increased up to 808 m2/g. All three MOF materials exhibit high chemical and thermal stability. JLU-MOF110(In) remains stable for 24 h at pH values ranging from 1 to 11, while JLU-MOF110(Fe) and JLU-MOF110(FeNi) persist to be stable for 24 h at pH from 1 to 12. JLU-MOF110(In) exhibits thermal stability up to 350 °C, whereas JLU-MOF110(Fe) and JLU-MOF(FeNi) can be stable up to 300 °C. Thanks to the microporous cage-based structure and abundant open metal sites, JLU-MOF110(In), JLU-MOF110(Fe), and JLU-MOF110(FeNi) have excellent CO2 capture capacity (28.0, 51.5, and 99.6 cm3/g, respectively, under 298 K and 1 bar). Interestingly, the ideal adsorption solution theory results show that all three MOFs exhibit high separation selectivity toward CO2 over N2 (35.2, 43.2, and 43.2 for CO2/N2 = 0.15/0.85) and CO2 over CH4 (14.4, 11.5, and 10.1 for CO2/CH4 = 0.5/0.5) at 298 K and 1 bar. Thus, all three MOFs are potential candidates for CO2 capture and separation. Among them, JLU-MOF110(FeNi) displays the best separation potential, as revealed by dynamic column breakthrough experiments.

Dependence of Transition-Metal Telluride Phases on Metal Precursor Reactivity and Mechanistic Implications.

Modern bottom-up synthesis to nanocrystalline solid-state materials often lacks the reasoned product control that molecular chemistry boasts from having over a century of research and development. In this study, six transition metals including iron, cobalt, nickel, ruthenium, palladium, and platinum were reacted with the mild reagent didodecyl ditelluride in their acetylacetonate, chloride, bromide, iodide, and triflate salts. This systematic analysis demonstrates how rationally matching the reactivity of metal salts to the telluride precursor is necessary for the successful production of metal tellurides. The trends in reactivity suggest that radical stability is the better predictor of metal salt reactivity than hard-soft acid-base theory. Of the six transition-metal tellurides, the first colloidal syntheses of iron and ruthenium tellurides (FeTe2 and RuTe2) are reported.

Scrutinizing the facile growth of β-Ag2Se fine films

Silver selenide thin film is one of the best candidates for thermoelectric devices. In the previous report, we demonstrated that high-performanced [201] oriented β-Ag2Se thin films can be prepared by direct metal surface element reaction (DMSER) solution selenization in a really short time at room temperature. However, the underlying mechanism of the fast reaction process were not discussed in depth. Herein, based on hard soft acid base (HASB) theory and strong oxidation, we further explored the possible reaction mechanism of the in-situ growth of β-Ag2Se thin films as the function of the reaction time. The time-dependent experimental results showed that the formation of the β-Ag2Se on elemental Ag precursor (∼690 nm thick) in Se/Na2S precursor solution is in a growth driven mode with no obvious orientation or growth rate selections to the elemental Ag precursors. Our investigations provide a prerequisite for the further preparation of thermoelectric materials with excellent properties.

Formation mechanism of a ternary nanohybrid based on magnetite-chitosan-graphene oxide according to HSAB theory

Magnetic nanohybrids containing chitosan (CS) and/or graphene have promising applications in environmental remediation. In this study, a ternary nanohybrid based on magnetite (M)-CS-graphene oxide (GO) (MCSGO) was prepared in a facile manner via simultaneous reduction–precipitation at room temperature. The as-prepared nanohybrid was characterized by field-emission scanning electron microscopy/energy dispersive X-ray spectroscopy, transmission electron microscopy, Raman spectroscopy, Brunauer–Emmett–Teller/Barrett–Joyner–Halenda analysis, thermogravimetric–differential thermal analysis, and vibrating sample magnetometry. Most importantly, the mechanism associated with the formation of MCSGO was determined using hard-soft acid-base (HSAB) theory and spectroscopic analyses. HSAB theory predicted the following dominant interactions in MCSGO based on electron transfer calculations and energy lowering between the couplet components: (1) CS-Fe3O4: NH2→Fe(III); (2) GO-Fe3O4: Ar-O-Ar→Fe(III); and (3) GO-CS: O(Ar-OH)→-OH (→ denotes the direction of electron flow and Ar denotes the aromatic ring). The CS-Fe3O4 and GO-Fe3O4 interactions were much stronger than that for GO-CS. The predictions obtained by HSAB theory were supported by X-ray photoelectron spectroscopy, Fourier transformation infrared spectroscopy, ultraviolet–visible spectra, and fluorescent spectra. According to HSAB theory and spectroscopic analyses, a mechanism was proposed for the formation of MCSGO based on electron transfer-induced energy lowering. In addition, MCSGO still adsorbed 199.41 mg g−1 and 193.96 mg g−1 of Hg(II) and Zn(II), respectively, after six consecutive cycles, thereby demonstrating its favorable removal efficiency. The results obtained in this study may facilitate the development of efficient adsorbents based on the MCSGO architecture for environmental remediation.

Facial design and synthesis of Ce doped Co-Ni oxide nanocages with cubic structure for high-performance asymmetric supercapacitors

From the perspective of nano science and nanotechnology, it is very interesting and important to develop a reasonable and practical synthesis route of nanomaterials for production and life. Here, we develop a strategy of hollow cubic metal oxide nanocages. The method was inspired by Pearson’s Hard-Soft-Acid-Base (HSAB) theory, and nanocages with excellent performance were prepared by coordination etching and optimization of reaction conditions. Firstly, Cu2O nanocubes were prepared by redox reaction at room temperature. Then, the hollow cubic NiCo2Ox/CeOy nanocages were obtained by HSAB theory and cerium doping. The nanomaterial has a specific capacitance of up to 1976 F/g at the current density of 1 A/g. In addition, the asymmetric supercapacitor (ASC) prepared with hollow cubic NiCo2Ox/CeOy nanocage as cathode and active carbon as anode exhibits an energy density as high as 37.1 Wh kg−1 at the power density of 375 W kg−1. The capacitance retention rate of the device is 91.5 % after 10,000 cycles. The device can be charged to light up LED lights. These excellent electrochemical properties, due to their unique structure and synergistic effect between materials, indicate the potential application value of hollow cubic NiCo2Ox/CeOy nanocages in high-performance supercapacitors.

Magnetic graphene oxide-chitosan nanohybrid for efficient removal of aqueous Hg(Π) and the interaction mechanism

Magnetic adsorbent combining graphene and chitosan have exhibited encouraging application in wastewater remediation. Herein, magnetic graphene oxide-chitosan nanohybrid (MGC) was readily obtained via synchronous reduction-precipitation under a mild experimental condition and utilized as adsorbent to remove aqueous Hg(Π). The interaction mechanism between MGC and Hg(Π) was unveiled via spectroscopic analyses, adsorption fittings and the hard-soft acid-base theory. Results present, 95 % of –NH2 in chitosan was transformed into –C(=O)NH– via amidation with –OH, enabling the outperformance of MGC over any single phase. MGC efficiently adsorbs 339.82 mg·g−1 of Hg(Π) in 8 min, during which the counterions in Hg(NO3)2·H2O were simultaneously adsorbed via chemical interaction featured by electron donation. Specifically, –C(=O)NH–, C–O and O2– contribute to Hg(Π) uptake, while Fe(III), Fe(Π) contribute to NO3– uptake. This work may provide inspiration for developing efficient adsorbent based on magnetic graphene oxide-chitosan.

Protic Ionic Liquids for Intrinsically Stretchable Conductive Polymers

Inspired by the classic hard-soft acid-base theory and intrigued by a theoretical prediction of spontaneous ion exchange between poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and hard-cation-soft-anion ionic liquid (IL), we treat PEDOT:PSS with a new IL composed of a protic (i.e., extremely hard) cation (3-methylimidazolium, p-MIM+) and an extremely soft anion (tetracyanoborate, TCB-). In fact, this protic IL (p-MIM:TCB) accomplishes the same levels of ion-exchange-mediated PEDOT-PSS separation, PEDOT-rich nanofibril formation, and electrical conductivity enhancement (∼2500 S/cm) as its aprotic counterpart (EMIM:TCB with 1-ethyl-3-methylimidazolium), the best IL used for this purpose so far. Furthermore, p-MIM:TCB significantly outperforms EMIM:TCB in terms of improving the stretchability (i.e., the highest tensile strain) of the PEDOT:PSS thin film. This enhancement is a result of the aromatic and protic cation p-MIM+, which acts as a molecular adhesive holding the exchanged ion pairs (PEDOT+:TCB----p-MIM+:PSS-) via ionic intercalation (at the surface of TCB--decorated PEDOT+ clusters) and hydrogen bonding (to PSS-), in which washing p-MIM+ out of the film degrades the stretchability while keeping the morphology. Our results offer molecular-level insight into the morphological, electrical, and mechanical properties of PEDOT:PSS and a molecular-interaction-based enhancement strategy that can be used for intrinsically stretchable conductive polymers.

Acetophenone protection against cisplatin-induced end-organ damage

Cisplatin is a widely used and efficacious chemotherapeutic agent for treating solid tumors, yet it causes systemic end-organ damage that is often irreversible and detrimental to quality of life. This includes severe sensorineural hearing loss, hepatotoxicity, and renal injury. Based on the hard-soft acid-base theory, we recently developed two acetophenone-derived, enol-based compounds that directly interfere with the side effects of cisplatin. We investigated organ-specific and generalized toxicity in order to define dose-dependent responses in rodents injected with cisplatin with or without the protective compounds. All metrics that were used as indicators of toxicity showed retention of baseline or control measurements when animals were pre-treated with acetophenones prior to cisplatin administration, while animals injected with no protective compounds showed expected elevations in toxicity measurements or depressions in measurements of organ function. These data support the further investigation of novel acetophenone compounds for the prevention of cisplatin-induced end-organ toxicity.

Manganese Molybdate Cathodes with Dual-Redox Centers for Aqueous Zinc-Ion Batteries: Impact of Electrolyte on Electrochemistry

Although bimetallic oxides have been shown to be beneficial as electrode materials in battery systems over their monometallic oxide counterparts, the implementation of metal molybdates with dual-redox centers has not been widely studied in aqueous rechargeable Zn-ion batteries. Manganese molybdate (MnMoO4) was synthesized via facile cosolvent coprecipitation and implemented as a cathode material for the first time in this system using 3 M ZnSO4 and 3 M ZnCl2 electrolytes to investigate the impact of the anion. In the two electrolytes, both manganese and molybdate metal centers were determined to be redox active using Mn and Mo K-edge operando X-ray absorption spectroscopies (XAS), with the corresponding voltage plateaus at 1.4 and 0.5 V, respectively. The difference in anions resulted in a preference regarding the active redox center, with the sulfate based preferring Mo redox and chloride based preferring Mn redox. Additionally, the redox reactions also differ in rate dependency, with Mn and Mo redox reactions preferring slow and fast current rates, respectively. In both systems, Mn redox was seen to be the more stable mechanism over prolonged cycling. The preference was related to the dissolution of the MnMoO4 material by applying Pearson’s hard–soft acid–base theory and considering the solubilities of the respective salts.

Incorporating hard-soft acid-base theory in multi-aspect analysis of the adsorption mechanism of aqueous heavy metals by graphene oxide

Water contamination by heavy metals is a serious environmental concern. To unravel the “species resolved” interaction mechanism of heavy metals with graphene oxide (GO), a multi-aspects analyses incorporating metal species distribution, GO surface charge, adsorption behavior and fitting, hard-soft acid-base (HSAB) theory, Fourier transformation infrared spectroscopy and X-ray photoelectron spectroscopy were performed. For pH 7 and T = 25 °C, adsorptions of aqueous Cd(Ⅱ) and Pb(Ⅱ) with equal initial concentrations of 300 mg L−1 by GO at 500 mg L−1 equilibrated in 15 min. The corresponding adsorption percentage and quantity for Cd(Ⅱ) were 98.04% and 588.22 mg g−1 and those for Pb(Ⅱ) were 92.10% and 552.56 mg g−1. When pH ≤ 7, bare Cd2+ and Pb2+ were the dominant metal species adsorbed by GO via ion exchange and chemical complexation. When pH ≥ 7, hydroxyl-complexed species were the dominant ones adsorbed by GO via precipitation, ion exchange, and chemical complexation. Electron transfer and energy lowering induced by the GO–heavy metal interaction, calculated based on HSAB theory, illuminated two points: (1) OH had a stronger binding affinity than COOH toward either Cd(Ⅱ) or Pb(Ⅱ) and (2) either OH or COOH had a stronger binding affinity toward Cd(Ⅱ) than Pb(Ⅱ). Explorations of this work may provide guidance in developing efficient graphene-based adsorbents for wastewater remediation.