Hard-soft Acid-base Principle Research Articles

Selective Recycling of Spent Lithium‐Ion Batteries Enables Toward Aqueous Zn‐Ion Batteries Cathode

AbstractEffective selective recycling of spent lithium‐ion batteries (S‐LIBs) and giving recycled products a “second life” are crucial for advancing energy supply circularity, environmental and economic sustainability development. However, separating metal compounds with similar charge differences requires substantial energy, water, and chemical inputs. Herein, an innovative strategy is present for selective recycling S‐LIBs by photoexcitation inspired by the Hard Soft Acid Base (HSAB) principle. Theoretical calculations and experimental results show that photoexcitation drives charge transfer and modulates subtle charge density differences among metal components, thereby enhancing their solubility disparity and facilitating metal separation. Remarkably, the photoexcitation‐induced metal separation factor reaches 46900 and the metal recovery efficiency approaches 100%, representing a significant improvement over non‐photoexcitation separation with a separation factor of non‐photoexcitation of merely 2.7. Through techno‐economic analysis, the viability of photoexcitation selective recycling technology has been confirmed as an eco‐friendly and economical approach for battery recycling. Furthermore, high‐value reuse of recovered Mn components is implemented. The Recycled Mn components are treated by calcination to obtain porous, defect‐rich Mn2O3, which showed a specific capacity of 613 mAh g−1 at 0.1 A g−1) in aqueous Zn‐ion batteries (AZIBs). This work provides fresh insight into recycling S‐LIBs and moving toward more sustainable storage technologies.

Air-Stable Li2S Cathodes Enabled by an In Situ-Formed Li+ Conductor for Graphite-Li2S Pouch Cells.

Using Li2S cathodes instead of S cathodes presents an opportunity to pair them with Li-free anodes (e.g., graphite), thereby circumventing anode-related issues, such as poor reversibility and safety, encountered in Li-S batteries. However, the moisture-sensitive nature of Li2S causes the release of hazardous H2S and the formation of insulative by-products, increasing the manufacturing difficulty and adversely affecting cathode performance. Here, Li4SnS4, a Li+ conductor that is air-stable according to the hard-soft acid-base principle, is formed in situ and uniformly on Li2S particles because Li2S itself participates in Li4SnS4 formation. When exposed to air (20% relative humidity), the protective Li4SnS4 layer maintains its components and structure, thus contributing to the enhanced stability of the Li2S@Li4SnS4 composite. In addition, the Li4SnS4 layer can accelerate the sluggish conversion of Li2S because of its favorable interfacial charge transfer, and continuously confine lithium polysulfides owing to its integrity during electrochemical processes. A graphite-Li2S pouch cell containing a Li2S@Li4SnS4 cathode is constructed, which shows stable cyclability with 97% capacity retention after 100 cycles. Hence, combining a desirable air-stable Li2S cathode and a highly reversible Li-free configuration offers potential practical applications of graphite-Li2S full cells.

Anion Exchange Membrane Using Fused Expanded Pyridinium As Their Cationic Unit

Ion conductivity is expressed as a function of the Faraday constant, ion concentration, and mobility. Thus, an increase in both ion concentration and mobility is crucial for increasing the ion conductivity. Ion mobility reflects ionic motion in the restricted area of ion conduction channels. The general approach to expand ion conduction channels in AEM is to introduce a large number of ionic groups, i.e., to increase ion-exchange capacity (IEC). Because the increase of IEC also increase ion concentration, increase of IEC have been major strategy for increasing ion conductivity. However, this approach causes softening of the AEM because high IEC involves large amount of water uptake (WU).On the other hand, the ion concentration in AEM is also affected by the dissociation constant of the ionic groups. However, conventional ionic groups in AEMs, such as ammonium cations, suffer from a low dissociation constant that leads to low ion conduction in AEM. Previously, we found that a fused expanded pyridinium cation (FEP) having a delocalized positive charge showed high dissociation of OH– owing to the weak interaction between the soft acid (FEP) and the hard base (OH–) which can be explained based on the Pearson Hard Soft Acid Base (HSAB) principle. As the result, AEM with FEP unit exhibited excellent ion conductivity of 123.4 ±13.3 mS cm–1 at 80 °C with very low IEC (0.77 mmol g-1).Recently, we synthesized alkylated fused expanded pyridinium (CxFEP) with alkyl chain lengths (x) of 0, 6, 12, and 18 and introduced into polymers as side chains for AEM applications. FEP is characterized by a large π cation that offers weak electrostatic interactions with anions such as hydroxide (OH–) ions and therefore leads to high OH– conductivity in AEM. CxFEP shows synergetic effect between the π-π interactions of FEP and van der Waals interactions of the alkyl chains and forms a strong assembly, particularly for C6FEP. On the other hand, when CxFEP was introduced into the polymers, C12FEP formed an ordered stacking assembly in the films, whereas the other polymers with shorter (C0 and C6) and longer (C18) alkyl chains exhibited no such ordered structure. For the AEM, all the polymers showed higher ion conductivities than that of commercial ammonium-based AEM, even with their low ion exchange capacities (IEC), probably because of their characteristic weak interactions between the FEP cation and OH–. In particular, the AEM with C12FEP showed the highest ion conductivity of 143.3 ± 27.3 mS cm-1 even with a very low IEC of 0.41 mmol g-1. In addition to the high ion dissociation of FEP, the molecular assembly of FEP provides ionic conduction paths. This study demonstrates the importance of high ion dissociation and formation of a conduction pathway for AEM with high conductivity.

Stiff, tunable and reprocessable polythiourea supramolecular materials by manipulating hydrogen-bonding and metal-coordinating interactions

Rational strategies manipulating hydrogen-bonding and metal-coordination interactions accelerate the development of supramolecular materials with unprecedented properties, such as adaptability, self-healing, stimuli-responsiveness, reprocessability and recyclability. Herein, supramolecular interactions of thioureas were fully utilized to design new materials with adjusted mechanical performances and robust reprocessability. A series of polythioureas were facilely synthesized by the co-polycondensation of CS2 and two diamines, which was an efficient and economical alternative to the isothiocyanate-based polymerization. Hydrogen-bonded polythiourea materials with tunable mechanical performances were achieved by adjusting the density and regularity of thiourea units in the polymer chains. Further incorporating tiny amount of metal salts (CuCl2, CuCl, CuBr and CuI) resulted in polythiourea materials with enhanced mechanical performances, following the trend determined by the hard-soft acid-base principle. As far as we know, this is the first report of metal-coordinated polythiourea supramolecular materials. The exploration of hard-soft acid-base principle will also provide new inspirations for designing metal-coordinated supramolecular materials.

Application of the hard‐soft acid–base principle in plasma‐in‐liquid processing

AbstractPlasma, owing to its reactivity and nonequilibrium properties, is a unique field commonly used in material processing. In recent years, plasma processing with a liquid phase has attracted considerable attention owing to its important advantages, such as high electron density and the availability of a wide variety of reactions in solutions. However, plasma‐in‐liquid material synthesis is occasionally difficult to control and guidelines are lacking. In this study, we investigated whether the hard‐soft acid–base (HSAB) principle, which is often applied in material synthesis, is applicable to the plasma‐in‐liquid process and demonstrated that organic solvent‐derived substances produced by plasma‐in‐liquid processing reacted with solutes according to the HSAB principle. These results suggest that the HSAB principle may apply to plasma‐in‐liquid processing.

High efficiency removal of methyl blue using phytic acid modified graphene oxide and adsorption mechanism

Phytic acid modified graphene oxide (PGO) has encouraging prospect in environmental application. Herein, PGO was fabricated with a simple hydrothermal method and used as adsorbent to remove methyl blue (MB). Elaborate inspection based on the hard-soft acid-base (HSAB) principle, spectroscopic characterization, as well as batch adsorption and fitting were conducted to unravel the adsorption mechanism. Results show, PGO efficiently adsorbs 89.08 mg·g−1 of MB in 22 min. HSAB principle proposes, high electron transfer (ΔN) and energy lowering (ΔE) induce covalent bond (chemical interaction), while low ΔN and ΔE induce electrostatic effect (physical interaction). Accordingly, both the first and second strongest interaction occurs between PA moiety and MB: π electrons of MB flows towards O atom in OH and O(–O–) of PA, respectively. Yet the third strongest interaction happens between GO moiety and MB: electron of O atom in OH group of GO flows towards N atom of MB. Above top three interactions are characterized by prominent ΔN and ΔE implying the formation of covalent bond. However, other interactions yield low ΔN and ΔE, suggesting the presence of electrostatic effect. HSAB principle conclusion was substantiated by FTIR and UV–Vis analyses. These findings confirm that PA modification enhances the adsorption affinity of graphene oxide. Thereby, chemical adsorption induced by physical interaction is proposed. This work may inspire the design of efficient adsorbent based on PGO framework for environmental restoration.

Computational Modeling of Gold Nanoparticle Interacting with Molecules of Pharmaceutical Interest in Water.

We derived a theory of biomolecule binding to the surface of Aun clusters and of the Au plane based on the hard soft acid base (HSAB) principle and the free electron metallic surface model. With the use of quantum mechanical calculations, the chemical potential (μ) and the chemical hardness (η) of the biomolecules are estimated. The effect of the gold is introduced via the empirical value of the gold chemical potential (-5.77 eV) as well as by using the expression (modified here) for the chemical hardness (η). The effect of an aqueous environment is introduced by means of the ligand molecular geometry influenced by the PCM field. This theory allows for a fast and low-cost estimation of binding biomolecules to the AuNPs surface. The predicted binding of thiolated genistein and abiraterone to the gold surface is about 20 kcal/mol. The model of the exchange reaction between these biomolecules and citrates on the Au surface corresponds well with the experimental observations for thiolated abiraterone. Moreover, using a model of the place exchange of linear mercaptohydrocarbons on 12-mercaptododecane acid methyl ester bound to the Au surface, the present results reflect the known relation between exchange energy and the size of the reagents.

Transformation of K2Sb8Q13 and KSb5Q8 Bulk Crystals to Sb2Q3 (Q = S, Se) Nanofibers by Acid-Base Solution Chemistry.

The ability to manipulate crystal structures using kinetic control is of broad interest because it enables the design of materials with structures, compositions, and morphologies that may otherwise be unattainable. Herein, we report the low-temperature structural transformation of bulk inorganic crystals driven by hard-soft acid-base (HSAB) chemistry. We show that the three-dimensional framework K2Sb8Q13 and layered KSb5Q8 (Q = S, Se, and Se/S solid solutions) compounds transform to one-dimensional Sb2Q3 nano/microfibers in N2H4·H2O solution by releasing Q2- and K+ ions. At 100 °C and ambient pressure, a transformation process takes place that leads to significant structural changes in the materials, including the formation and breakage of covalent bonds between Sb and Q. Despite the insolubility of the starting crystals in N2H4·H2O under the given conditions, the mechanism of this transformation can be rationalized by applying the HSAB principle. By adjusting factors such as the reactants' acid/base properties, temperature, and pressure, the process can be controlled, allowing for the achievement of a wide range of optical band gaps (ranging from 1.14 to 1.59 eV) while maintaining the solid solution nature of the anion sublattice in the Sb2Q3 nanofibers.

Unique Microstructures and High Thermoelectric Performance in n–type Bi2Te2.7Se0.3 by the Dual Incorporation of Cu and Y

n-type thermoelectric systems operating near ambient temperature have been significantly understudied. n-type Bi2Te3-based materials have suffered from lack of efficient performance-enhancing strategies and compositional diversity mainly due to the difficulty in efficient doping and alloying to their structure. Herein, we report new n-type thermoelectric system Bi2-xYxTe2.7Se0.3 (x = 0 – 0.020) and optimized Cu0.01Bi1.985Y0.015Te2.7Se0.3 involving unique yttrium selenide-based microstructures. The incorporated Y and Cu atoms serve multiple favorable roles in improving thermoelectric performance of the title samples. A majority of the introduced Y forms either semiconducting Y2Se3 or metallic Y5-δSe7 depending on its chemical pressure, significantly affecting both thermal and charge transport properties. Changing the Y concentration in the nominal composition dynamically changes the composition of the surrounding matrix, microstructures, and their interfaces. The generation of microstructures and compositional variance driven by the Y and Cu incorporation can be understood and controllable in light of hard-soft acid-base principle and structural chemistry of the constituent elements. Cu atoms are more abundant in the interface than the other areas, and richer inside the microscale precipitate than the surrounding matrix, thereby creating large mass and compositional fluctuation. The Raman spectra verify that the incorporated Y and Cu atoms contribute to scattering and softening phonon modes effectively. All these jointly depress the lattice thermal conductivity of the optimized phase Cu0.01Bi1.985Y0.015Te2.7Se0.3 to ∼0.51 W m-1 K-1 at 300 K. The dual incorporation of Cu and Y atoms induces heavier density of states effective mass, thereby improving a magnitude of Seebeck coefficients. Accordingly, power factor increases especially near room temperature, giving ∼39.1 μW cm-1 K-2 at 300 K. Consequently, the Cu0.01Bi1.985Y0.015Te2.7Se0.3 sample achieves a high thermoelectric figure of merit, ZT, of ∼1.20 at 347 K and an average ZT of ∼1.16 from 300 to 423 K. Its ZT of ∼1.09 at 300 K is comparable to the state-of-the-art n-type polycrystalline Bi2Te3 systems.

Free radical induced degradation and computational studies of hydroxychloroquine in aqueous solution

Hydroxychloroquine (HCQ) is a potential drug molecule for treating malaria. Recently it has also been tried as adjustment in Covid 19 therapy. Interaction of HCQ with free radicals is very important, which controls its stability in the environment where free radicals are generated unintentionally. In this report, we present detailed investigation on the reactions of hydrated electrons (eaq−) and hydroxyl radical (•OH) with HCQ in aqueous solution through electron pulse radiolysis technique and computational studies. The degradation of HCQ was found to be faster in the case of reaction with •OH radicals. However, the degradation could be substantially slowed down in the presence of antioxidants like ascorbic acid and gallic acid. This revealed that the stability of HCQ could be enhanced in an oxidative environment in the presence of these two compounds, which are easily available through food supplements. Various global and local reactivity parameters are also determined to understand the reactivity trend using Hard-Soft Acid-Base (HSAB) principle in the realm of the DFT methods. Computational studies were performed to elucidate the site-specific reactivity trend towards the electrophilic and nucleophilic attack by calculating the condensed Fukui index for various species of HCQ.

Single Platinum Atom Catalysts with HighDensity.

As a new frontier, the rapid development of single-atom catalysts (SACs) in heterogeneous catalysis has attracted extensive attention. However, a fundamental understanding of the dynamic formation process of active metal atom sites is lacking. The rational design of high-performance SACs now becomes possible byexplicitly addressing the conundrum of constructing high-density SACs and elucidating the evolution of SACs during the synthesis.

Design and oxidative desulfurization of Ag/Ti heterometallic clusters based on Hard-Soft Acid-Base principle.

Hard-Soft Acid-Base (HSAB) principle plays an important guiding role in the design and synthesis of novel clusters and coordination compounds, in which "soft acids prefer to react with soft bases, while hard acids have an affinity for hard bases". Based on HSAB principle, four Ag/Ti heterometallic clusters, including Ag2Ti10, Ag2Ti11 with "Ti-encapsulated Ag" configurations, and two "Ag-encapsulated Ti" structures Ag2Ti2 and Ag2Ti12, were synthesized under solvothermal conditions. In addition, Ag2Ti12 exhibited an efficient and stable catalytic activity for sulfide oxidation. This work provides not only a new structural model for the modulation of the catalytic oxidative desulfurization properties of Ag/Ti heterometallic clusters but also a new insight of the utilization of phosphine-containing ligands to regulate the structure of Ag/Ti heterometallic clusters.

Ligands as “Matchmakers”: Alloying from a Physical Mixture of Metal Nanoparticle Dispersions by Digestive Ripening

Digestive ripening (DR) of a physical mixture of different metal nanoparticles (NPs) in the presence of a suitable ligand is demonstrated to be a convenient way to obtain alloy NPs. The results show that the right choice of metal-ligand combination is extremely important for efficient alloying. The results are rationalized on the basis of hard soft acid base principles, and it is concluded that better alloying ensues if DR is carried out with soft ligands when soft metals are being used and hard ligands facilitate alloying between hard metals. On the other hand, when a physical mixture of hard-soft metals is taken, ligands with intermediate character work better. The results presented here could prove to be extremely valuable and open new avenues of making interesting alloy/intermetallic systems.

Efficient separation of hard actinides from rare earths using the functionalised silica gels

Separation of hard actinides from rare earth metal ions is one of the challenging task as both these types of ions are hard ions. Therefore, from the view point of Hard-Soft Acid-Base principle, selecting suitable ligands is beyond the conventional procedure for their successful separation. Herein, we have proposed two oxygen donating ligands namely 1,8-dihydroxyanthraquinone functionalised silica gel (DHAFSG) and pyridine-N-oxide functionalised silica gel (PNOFSG). They have been synthesized, characterised and tested for the separation of hard actinides e.g. UO22+, Th4+ from rare earths. Interestingly, it has been found that the anions present in the aqueous medium controls the complexation and binding of the metal ions with the adsorbents. Rare earths are more selectively extracted from nitrate-carbonate medium giving the separation factors of 9 and 12 from actinides using DHAFSG and PNOFSG adsorbents respectively. Whereas, from pure nitrate medium, the hard actinides are selectively extracted and the separation factors for Th4+ from rare earths are 1000 and 4000 using PNOFSG and DHAFSG adsorbents respectively in pure nitric acid medium at pH 1. Kinetics of adsorption is fast in all the cases using DHAFSG and PNOFSG adsorbents. The performances of DHAFSG and PNOFSG have been tested for the separation of actinides from rare earths in Simulated Monazite ore Solution (SMS) in nitric acid medium. Selective separation of actinides from the rare earth elements from SMS has been obtained.

Metal-Ion Coupling in Metal-Organic Framework Materials Regulating the Output Performance of a Triboelectric Nanogenerator.

Metal-organic frameworks (MOFs) as friction nanopower generation materials have attracted more and more research and attention because of the inherent three-dimensional framework structure and large aperture. In this work, the ZUT-75(Mn) with a one-dimensional pore structure was synthesized by using electron-rich benzimidazole carboxylic acid ligands, and isomorphic offspring MOF materials were obtained by single crystal-single crystal solvent-assisted metal-ion exchange. The exchange process was monitored by liquid UV-vis spectroscopy, atomic absorption spectrometry, and energy-dispersive X-ray spectroscopy. The metal-oxygen coordination energy, X-ray photoelectron spectroscopy binding energy, and hard-soft acid-base principle verified the spontaneity of the central-metal-exchange reaction. The four materials were applied to a triboelectric nanogenerator (TENG), and the output performance law of ZUT-75 was Co-MT > Zn-MT > Cu-MT > Mn-MT. Among them, the charge and power densities of Co-MT were up to 127.05 μC m-2 and 3280.50 mW m-2. When the density functional theory calculation and variable-temperature magnetic susceptibility test results were combined, it was concluded that low metal-ion-coupling degree promoted the formation and transfer of contact electrifications, which greatly improved the output performance of the TENG. This work provided a new idea for improving the output performance of the TENG.

Insight into generalized local softness based on ABEEM‐σπ method: Electrophilic additions to alkenes

AbstractAccording to the local hard‐soft acid – base (HSAB) principle, the generalized local softness has been investigated based on the electrophilic reactions of H2O, HF, HCl and HBr to alkenes, and the effect of the softness on the chemical reactivity was studied in terms of the ab initio and atom‐bond electronegativity equalization method plus σπ (ABEEM‐σπ) method. Studies show that the finite difference approximation with ab initio method cannot always be used to predict the regioselectivity of the investigated reactions in terms of the local HSAB principle. But ABEEM‐σπ model could well describe chemical reactivity according to the local HSAB principle. A significant characteristic of the ABEEM‐σπ method is that the double bond is explicitly considered and partitioned. The square sums of differences of the local softness of the reaction center atoms, that is, Δs, or ΔSG with the generalized local softness and with the electronegativity, have been studied on the considered electrophilic additions. Studies indicate that ΔSG can be utilized not only to predict regioselectivity rules but also to rationalize the chemical reactivity of these addition reactions, and the generalized local softness is more suitable for the investigation of chemical reactivity between two chemical species.

Hard-Soft Chemistry Design Principles for Predictive Assembly of Single Molecule-Metal Junctions.

The achievement of atomic control over the organic-inorganic interface is key to engineering electronic and spintronic properties of molecular devices. We leverage insights from inorganic chemistry to create hard-soft acid-base (HSAB) theory-derived design principles for incorporation of single molecules onto metal electrodes. A single molecule circuit is assembled via a bond between an organic backbone and an under-coordinated metal atom of the electrode surface, typically Au. Here, we study molecular composition factors affecting the junction assembly of coordination complexes containing transition metals atoms on Au electrodes. We employ hetero- and homobimetallic lantern complexes and systematically change the coordination environment to vary the character of the intramolecular bonds relative to the electrode-molecule interaction. We observe that trends in the robustness and chemical selectivity of single molecule junctions formed with a range of linkers correlate with HSAB principles, which have traditionally been used to guide atomic arrangements in the synthesis of coordination complexes. We find that this similarity between the intermolecular electrode-molecule bonding in a molecular circuit and the intramolecular bonds within a coordination complex has implications for the design of metal-containing complexes compatible with electrical measurements on metal electrodes. Our results here show that HSAB principles determine which intramolecular interactions can be compromised by inter molecule-electrode coordination; in particular on Au electrodes, soft-soft metal-ligand bonding is vulnerable to competition from soft-soft Au-linker bonding in the junction. Neutral donor-acceptor intramolecular bonds can be tuned by the Lewis acidity of the transition metal ion, suggesting future synthetic routes toward incorporation of transition metal atoms into molecular junctions for increased functionality of single molecule devices.

Ultra-deep removal of Pb by functionality tuned UiO-66 framework: A combined experimental, theoretical and HSAB approach

A specific functionality in the adsorbent materials plays a significant role for the selective capture of heavy metals based on Pearson's Hard-Soft-Acid-Base (HSAB) concept. Herein, we introduced single and double amino- and thiol-functionalities into the UiO-66 framework, which acted as hard and soft base sites for heavy metal adsorption, respectively. The synthesized adsorbents (labelled as NH2-UiO-66, (NH2)2-UiO-66, SH-UiO-66 and (SH)2-UiO-66) were applied for the selective removal of lead (Pb) ions from contaminated water. The removal efficiency of Pb was about 64, 85, 75 and 99% (pH = 6, T = 30 °C, sample dosage = 10 mg, Pb concentration = 100 mg L−1), respectively, based on available number of interacting sites in the respective adsorbent. To elaborate HSAB concept, the interacting sites of these functional groups towards Pb were explored by identifying their possible types of interactions in terms of soft acid-base affinity, coordinate and covalent bonding, chelation, π-π interactions and synergetic effect of bonding. Density functional theory (DFT) simulation was used to confirm these interactions and to help the better understanding of adsorption mechanism. Model fitting and characterization of Pb-sorbed adsorbents were also performed to reveal kinetics, order of adsorptive reaction, thermodynamics and adsorption mechanism. Moreover, the optimization of adsorptive removal was performed by controlled parameters including time, initial concentration, pH and temperature. The reusability and selectivity of these adsorbents along with recovery of Pb(II) were also assessed. This study presents the conceptual framework for the design of functional adsorbents in the removal of heavy metals using the HSAB principle as an intended guideline.

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed‐Anion Lanthanide Oxyhalides

AbstractA challenge in anion control in periodic solids is to preserve the crystal lattice while substituting for different anions of widely varying size and hardness. Post‐synthetic modification routes that place cations or anions in non‐equilibrium configurations are promising; however, such methods remain relatively unexplored for anion placement. Here, we report the synthesis of LaOI nanocrystals by a non‐hydrolytic sol‐gel condensation reaction and their transformation into LaOBr, LaOCl, and LaOF nanocrystals along hard–soft acid–base principles using post‐synthetic metathesis reactions with ammonium halides. Anion displacement proceeds along halide planes, preserving the tetragonal matlockite structure. Energy‐variant X‐ray excited optical luminesce signatures of alloyed Tb3+‐ions is a sensitive quantum reporter of the preservation of the cation sublattice and hardening of the crystal structure upon anion replacement.

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed-Anion Lanthanide Oxyhalides.

A challenge in anion control in periodic solids is to preserve the crystal lattice while substituting for different anions of widely varying size and hardness. Post-synthetic modification routes that place cations or anions in non-equilibrium configurations are promising; however, such methods remain relatively unexplored for anion placement. Here, we report the synthesis of LaOI nanocrystals by a non-hydrolytic sol-gel condensation reaction and their transformation into LaOBr, LaOCl, and LaOF nanocrystals along hard-soft acid-base principles using post-synthetic metathesis reactions with ammonium halides. Anion displacement proceeds along halide planes, preserving the tetragonal matlockite structure. Energy-variant X-ray excited optical luminesce signatures of alloyed Tb3+ -ions is a sensitive quantum reporter of the preservation of the cation sublattice and hardening of the crystal structure upon anion replacement.