Valence State Research Articles

Bimetallic MnZn-MOF-74 with enhanced percentage of MnIII: Efficiently catalytic activity for direct oxidative carboxylation of olefins to cyclic carbonates under mild and solvent-free condition

Multi-functional MOF catalyst with oxidative- and acid- centers showed potential in olefins oxidative carboxylation to cyclic carbonates directly. In this work, a series of bimetallic MnZn-MOF-74 with different molar ratios of Mn and Zn were synthesized successfully through a one-pot facile method. Thoroughly characterization indicated that the existence of Zn regulated the valance state distribution of Mn in the obtained MnZn-MOF-74. Mn99.3Zn0.7-MOF-74 with the highest ratio of MnIII (61.3 %) performed the most efficient activity for olefin direct tandem oxidative carboxylation reaction using aqueous tert-butyl hydroperoxide oxidant under solvent-free condition of 90 °C, 1.0 MPa CO2 and 4 h. Mn99.3Zn0.7-MOF-74 also showed satisfactory versatility and recyclability. Based on the experiments, a feasible mechanism was presented. Thanks to the high ratio of active MnIII as main oxidative center, the coordination unsaturated bimetal Mn and Zn as Lewis-acid sites, O2– of metal − O as Lewis-base sites and combined effect with Bu4NBr cocatalyst, Mn99.3Zn0.7-MOF-74 presented efficient performance for the direct synthesis of cyclic carbonates from olefins. The metal Zn in MOF can regulate the valance state distribution of Mn and result in efficient catalytic property, presenting a potential avenue for direct oxidative carboxylation reaction of olefins to cyclic carbonates synthesis.

Fabrication, characterization, and in vitro studies of Selenium-substituted hydroxyapatite coatings

Abstract The increasing demand for hydroxyapatite (HA) coatings with enhanced functionality have led to novel materials with compositions that are more closely resembling those of natural bone apatites. In the present study, selenium-substituted (Se–HA) powders with various Se quantities were prepared by chemical precipitation. By applying suspension plasma spray (SPS), the surface of Ti substrates was coated with corresponding Se-HA coatings. The microstructural and physicochemical properties of the powders and the coatings were studied. Analysis by X-ray diffraction indicates that SeO32− replaced the PO43− groups, affecting the crystal structure and crystallinity of HA. As the extent of Se substitution increases, the lattice volume expands and the crystallinity decreases. The synthesized Se–HA powders were confirmed to be calcium-deficient apatite through energy-dispersive X-ray spectroscopy. However, the high temperature of SPS accelerated volatilization of P, increasing the Ca/(P + Se) ratio of the coatings, whereas the chemical valence state of Se remained unchanged. The Se–HA coating exhibited a high bonding strength of >33 MPa, fully meeting the requirement of 15 MPa as coating implant materials. Dissolution behavior tests indicate that the Se–HA coatings had high solubility in comparison to the HA coating. As the substitution degree of Se increased, the dissolution rate also increased, which greatly enhanced the capacity to generate a bone-like apatite layer. In vitro cell experiments indicate that the Se–HA coatings exhibited excellent biocompatibility, and facilitated adhesion and proliferation of osteoblast MC3T3-E1, even in the presence of fluorine. Furthermore, antibacterial properties of Se–HA coatings were also indicated by inhibition of Staphylococcus aureus, which is the main cause of most infections after orthopedic surgeries. Thus, the Se–HA coatings have potential as implant coating materials for orthopedic applications.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters

The selective synthesis of valuable azo‐ and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine‐tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF‐8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) catalyzed nitrobenzene reduction to azobenzene. X‐ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO‐DRIFTS) of Au NC/ZIF‐8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF‐8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF‐8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure‐selectivity relationships.

Unveiling the Unique Reactivity of Anionic Mn(I) Complexes via Metal-Ligand Cooperation: Nucleophilic Attack on C(sp3)-X Bonds.

Metal-ligand cooperation (MLC) has emerged as a pivotal strategy for the catalytic activation of small molecules within both synthetic and biological arenas. Leveraging this approach, a suite of potent catalytic reactions─encompassing hydrogenation, hydroelementation, and dehydrogenative processes─have been realized, with notable advances in manganese catalysis in recent years. However, the activation of alkyl halides by Mn complexes, which typically requires strong reductants to form Mn(-I) complexes that are incompatible with standard cross-coupling conditions, remains a significant challenge. This limitation underscores the urgent need to investigate alternative methods for activating C(sp3)-X bonds using higher valence state Mn complexes. In response to this challenge, we present the synthesis, characterization, and reactivity of a new anionic Mn(I) complex featuring a redox-active dianionic ligand that induces multiple MLC functionalities. We have discovered an innovative mechanism of MLC, characterized by a single ligand transferring two electrons to the metal center. This novel process facilitates an orbital-symmetry-allowed nucleophilic attack on C(sp3)-X bonds, preserving manganese's oxidative state at +1. To the best of our knowledge, this is the first instance where the MLC strategy via a two-electron transfer process has been utilized to execute an SN2 nucleophilic attack at a C(sp3)-X bond by a relatively electron-deficient metal center like Mn(I). Additionally, the dianionic ligand of the anionic Mn(I) complex exhibits ambident nucleophilicity by reacting with different electrophiles, further highlighting its versatile reactivity.

Synergistic interface engineering of ZnCo2O4/NiMnCo-layered double hydroxides for boosted reactivity in advanced supercapacitor electrodes

NiMn layered double hydroxide (LDH) exhibits high redox activity as a cathode material for hybrid supercapacitors, but it has the disadvantages of low conductivity and poor stability. In this work, the electrochemical properties of NiMnCo-LDH with different Co contents prepared by electrodeposition were tested. The results showed that the addition of an appropriate amount Co increased the adsorption of OH− on NiMn-LDH and improved the reactivity of the material. ZnCo-MOF grown on carbon cloth was transformed into flake ZnCo2O4 by calcination, and NiMnCo-LDH was electrodeposited on it to prepare ZnCo2O4/NiMnCo-LDH composite electrode. The core-shell structure increases the reaction area between the LDH material and the electrolyte. Physical characterization and density functional theory (DFT) calculations show that the structure and electronic distribution of ZnCo2O4/NiMnCo-LDH at the heterogeneous interface are reconstructed, which increases the valence state of Co and Mn elements, and finally exhibits enhanced electrochemical performance. Due to the existence of this synergistic effect, the specific capacity of the electrode is as high as 231.5 mAh g−1, with excellent stability demonstrated after 5000 cycles compared to the NiMnCo-LDH. The assembled hybrid supercapacitor exhibits a high energy density of 39.4 Wh kg−1, and has high cycle stability (90 % after 5000 cycles).

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters.

The selective synthesis of valuable azo- and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine-tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF-8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs)catalyzed nitrobenzene reduction to azobenzene. X-ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO-DRIFTS) of Au NC/ZIF-8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF-8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF-8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure-selectivity relationships.

Organization of A2‐Type Active Composite Nanorods

AbstractNanorods as building blocks are promising to construct functional superstructures. A paramagnetic Fe3O4‐based composite nanorod is large‐scale synthesized from the poly(2‐vinylpyridine) (P2VP) side chain grafted polymer bottlebrush by electrostatics‐mediated intramolecular crosslinking via metallic coordination. Ultrasonication‐assisted fracturing of the composite nanorod derives the corresponding A2‐type composite nanorods whose two ends are active with the metallic coordinated P2VP exposed. The active ends are prone to connection upon feeding ligands (acidic or alkaline) or metallic ions to trigger the organization of the A2‐type nanorods toward functional superstructures. Their microstructure is tunable from linear nanowires to branches, which is dependent on the valent state of the assistant chemicals. The report method is easily extended to derive a family of A2‐type active nanorods with varied compositions and functions which are capable to organize functional nanomaterials with tunable microstructure.

Sn2+/Pb2+ Doping‐Induced Highly Transparent Boroaluminate Microcrystalline Glass With Deep Traps for Long‐Term Optical Storage and Time‐Lapse X‐ray Imaging

AbstractThe development of microcrystalline glass‐ceramics with high transparency and deep trap energy levels is crucial for the cost‐effective and large‐scale production of scintillators and optical data storage applications. In this study, the incorporation of highly electronegative divalent tin (Sn2+) plays a key role in modulating the network structure of borate glass. This leads to the successful synthesis of SrAl2O4:Eu2+ microcrystalline glass with high transparency, reaching up to 80%, and excellent crystallinity. Additionally, a series of non‐optically active ions with different valence states is co‐doped with Eu2+ to fine‐tune the trap levels of the SrAl2O4 microcrystals. All samples maintain high crystallinity and exhibit good transparency. In particular, the Pb2+ ion co‐doped samples achieve an increased trap energy level of 1.28 eV, significantly enhancing their capacity to capture X‐rays and ultraviolet light. Density functional theory calculations reveal that this enhancement is due to severe lattice distortion caused by Pb2+ ions occupying interstitial sites in SrAl2O4. Utilizing the SrAl2O4:Eu2+, Pb2+ glass‐ceramics materials, X‐ray imaging with a delay of up to 210 s and optical information storage for >60 d is achieved. This study provides valuable insights into the crystal growth and trap modulation of persistent luminescent materials within a three‐dimensional glass network structure.

Modulating the Structural and Electrical Properties of SrFeO3-δ by A-site alkali metal ion doping

Abstract The electrical properties of perovskite structured SrFeO3-δ can be modulated by A site doping. The present work focuses on the influence of concentration and ionic radii of alkali metal cation on the structural and electrical properties of Sr1-xAxFeO3-δ (A= Ca, Ba and x = 0, 0.25, 0.50, 0.75). The X-ray diffraction studies confirm the phase change from cubic to orthorhombic with Ca content while orthorhombic to cubic structural translation was observed with Ba concentration. A lattice contraction and expansion were observed for doping depending on the ionic radii of dopant cation. The X-ray photoelectron spectroscopy results indicate the presence of Fe in mixed valence state of +2, +3, +4 state and adsorbed oxygen content was found to be higher upon Ba doping than that of Ca. A maximum conductivity of 1.82 x10-3 Scm-1 (x = 0.25) and 5.31 x10-3 Scm-1 (x=0.5) was observed at 800°C for Ca and Ba doped samples, respectively, one order higher than the base SrFeO3- δ. Thus, our results emphasise the importance of dopant addition on tailoring the electrode properties for SOFC application.

Few-femtosecond soft X-ray transient absorption spectroscopy with tuneable DUV-Vis pump pulses

Achieving few-femtosecond resolution for a pump-probe experiment is crucial to measuring the fastest electron dynamics and for creating superpositions of valence states in quantum systems. However, traditional UV-Vis pump pulses cannot achieve few-fs durations and usually operate at fixed wavelengths. Here, we present, to our knowledge, an unprecedented temporal resolution and pump tuneability for UV-Vis-pumped soft X-ray transient absorption spectroscopy. We have combined few-fs deep-UV to visible tuneable pump pulses from resonant dispersive wave emission in hollow capillary fiber with attosecond soft X-ray probe pulses from high harmonic generation. We achieve sub-5-fs time resolution, sub-fs interferometric stability, and continuous tuneability of the pump pulses from 230 to 700 nm. We demonstrate that the pump can initiate an ultrafast photochemical reaction and that the dynamics at different atomic sites can be resolved simultaneously. These capabilities will allow studies of the fastest electronic dynamics in a large range of photochemical, photobiological and photovoltaic reactions.

Piezoelectric Ceramic Hardening Through Defect Distribution Optimization in Multicomponent Systems

AbstractAcceptor doping is a common method for hardening modified piezoelectric ceramics. The mechanism through which the hardening effect can be improved has been widely studied and verified. However, the effect of defects caused by different valence states of the B‐site ions on the properties of multicomponent piezoelectric ceramics remains to be discussed. Therefore, in this work, a novel Pb(Ni1/3Nb2/3)O3–Pb(In1/2Nb1/2)O3–Pb(Mn1/3Nb1/2)–PbTiO3 quaternary hard ceramic with excellent performance is prepared and studied. The interaction between grain‐boundary defects and defect dipoles is proposed to be the mechanism behind the observed excellent performance. It is found that different types of defects improve the hardening effect in various ways. These results can provide a theoretical basis for the preparation of multicomponent piezoelectric ceramics with better properties.

Unusually improved peracetic acid activation for ultrafast organic compound removal through redox-inert Mg incorporation into active Co3O4

Peracetic acid (PAA) is increasingly used in advanced oxidation processes (AOPs) for water purification, yet there remains a critical need for highly-efficient and low-cost activators. Here, we constructed abundant oxygen vacancies (OVs) into redox-active Co3O4 by incorporating redox-inert Mg species (MgCoOx), achieving ultrafast degradation of sulfamethoxazole (SMX) via PAA activation. The MgCoOx/PAA system successfully degraded SMX within 3 min, with a removal rate 154.8 times higher than the Co3O4/PAA system, surpassing even previously reported single-atom catalysts. The primary active species identified was the acetylperoxyl radical (CH3C(O)OO•), with CoIV-oxo acting as a secondary active species that produced 18O-labeled sulfone compounds. We proposed a novel mechanism involving redox-inert Mg species that simultaneously strengthened PAA adsorption and activation. The enriched surface hydroxyl groups after Mg incorporation elevated the affinity for PAA binding. Meanwhile, the reduced Co average valence state and enhanced electron transfer capability facilitated PAA activation. This study offers an in-depth knowledge of redox-inert alkaline earth metals in PAA-AOPs.

Combustion-explosion suppression and environmental protection of typical sulfur-containing hazardous chemicals.

Sulfur, as a crucial chemical raw, poses increased combustion-explosion risks when mixed with other hazardous substances due to its dual nature as both an oxidant and a reducing agent. Additionally, sulfur-induced combustion and explosions can result in environmental pollution. Combustion-explosion suppression technology plays a crucial role in industrial production by effectively preventing hazardous chemical explosion incidents. This research investigates the combustion-explosion suppression of black powder, a common hazardous chemical containing sulfur, by utilizing two solid-based blast suppressants, NH4H2PO4 and NaHCO3. On this basis, examining changes in the oxidation states of sulfur and explaining the mechanisms of combustion-explosion suppression through the examination of combustion-explosion products. Additionally, numerical calculations are employed to analyze the evolution patterns of gaseous and solid-phase products throughout the entire combustion-explosion process. Research indicates that NaHCO3 exhibits a more effective combustion-explosion suppression effect on black powder compared to NH4H2PO4, which attributed to the valence state transformation of sulfur and the reduction of carbon oxidation. Furthermore, with the enhancement of combustion-explosion suppression effect, K2S, which a pollutes the environment, is gradually transform converted into potassium fertilizer K2SO4, which benefits plants. These results offer new insights into the research of combustion-explosion suppression of sulfur-containing substances and environmental protection strategies.

Pleiotropy of biomineralized bacterial outer membrane vesicles in modulating immune systems for liver cancer therapy

The immune landscape of late-stage liver cancer is featured by severe immunosuppression that is characterized by poor immunogenicity, T-cell exhaustion, and infiltration of a large number of immunosuppressive cells, leading to compromised therapeutic efficacy of mainstream immunotherapies. Herein, we developed a pleiotropic immune cell mobilization strategy to modulate immune systems for immunosuppressive liver cancer therapy. In this study, immunogenic bacteria-derived outer membrane vesicles (OMVs) were exploited as a vector to deposit Cu and Mn with mixed valence states via one-step biomineralization, followed by platelet membrane camouflage, which are denoted as OPCM. Mechanistically, the pleiotropic OPCM possesses POD, CAT, and GPX-like activities, thereby achieving cGAS-STING activation, immunogenic ferroptosis, and tumor hypoxia alleviation, ultimately leading to initiation of the cancer immunity cycle, modulation of both innate and adaptive immune system, and reversion of immunosuppression. Notably, the combination with typical αPD-L1 treatment augmented the tumor suppression effect by amplifying the intensity of ferroptosis due to IFN-γ secretion by activated T cells. Overall, the metal biomineralized OPCMs in combination with αPD-L1 formed a closed-loop therapy that cycles from immunotherapy and ferroptosis therapy, providing new insights for treating immunosuppressive liver cancer.

Vacancy-rich heterogeneous MnCo2O4.5@NiS electrocatalyst for highly efficient overall water splitting

Alkaline water electrolysis is regarded as a promising technology for sustainable energy conversion. Spinel oxides have attracted considerable attention as potential catalysts because of their diverse metal valence states. However, achieving the required current densities at low voltages is a challenge due to its limited active sites and suboptimal electron transport. In this study, we present a novel bifunctional catalyst composed of MnCo2O4.5 nanoneedles grown on NiS nanosheets for water electrolysis. Remarkably, MnCo2O4.5@NiS demonstrates exceptional catalytic activity, requiring 187 and 288 mV to achieve a current density of 100 mA cm−2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. The impressive performance of MnCo2O4.5@NiS is demonstrated by the lower value of voltage 1.44 V needed to deliver the current density of 10 mA cm−2, which outperformed the 1.66 V required for a commercial Pt/C||RuO2 system. Detailed structure analysis and density functional theory (DFT) calculations reveal that the MnCo2O4.5@NiS heterostructure enhances electron transfer at the interface, promotes the formation of oxygen vacancies and tunes the electronic structures of Mn and Co. These findings underscore the potential of MnCo2O4.5@NiS as an efficient and cost-effective electrocatalyst for hydrogen production.

Photo-electrochemical sensor based on BiOI/ZnIn2S4 heterojunction for detecting hydrogen peroxide and dopamine.

Photoelectrochemical (PEC) detection as a potential development strategy for hydrogen peroxide and dopamine sensors has receivedextensive attentions. Herein, BiOI/ZnIn2S4-X (X = n (BiOI)/n(ZnIn2S4)) heterojunction was synthesized using various molar ratios via a two-step method. A series of characterization techniques were employed to analyze the composition, surface structure, valence state, and optical properties of BiOI/ZnIn2S4-X. The results show that BiOI/ZnIn2S4-X perform significantly better than both BiOI and ZnIn2S4. Furthermore, BiOI/ZnIn2S4-9% exhibits superior visible light absorption capacity and photocurrent response among all of the BiOI/ZnIn2S4-Xtested. Therefore, a PEC sensor was developed using BiOI/ZnIn2S4-9% for the detection of hydrogen peroxide and dopamine. The linear detection range for hydrogen peroxide spans from to 1 ~ 40,000 µM, with the LOD of 0.036 µM (S/N = 3). For dopamine, the corresponding values are 2 ~ 250 µM for the linear detection range, and 0.017 μM for the LOD, respectively. Thesensor exhibitsdemonstrates excellent stability, reproducibility and resistance to interference, enabling the detection of real samples and thus holds promising application potential.

Valence State Regulated Nickel Iron Layered Double Hydroxides by Amine Intercalation as Efficient Electrocatalysts for Seawater Oxidation

Valence State Regulated Nickel Iron Layered Double Hydroxides by Amine Intercalation as Efficient Electrocatalysts for Seawater Oxidation

NIR-II light-activated and Cu nanocatalyst-enabled bioorthogonal reaction in living systems for efficient tumor therapy

Bioorthogonal reaction refers to chemical reactions that occur within a biological system without interfering the normal biochemical process, offering the unprecedented versatility in engineering chemical reactions within cells. However, the precise regulation of bioorthogonal reaction in living systems is mired by the complexity of the physiological environment and the toxicity of catalysts. Herein, considering the deeper tissue penetration and reduced phototoxicity compared to visible light and ultraviolet, a second near infrared (NIR-II) light-activated Cu-based bioorthogonal reaction is developed to achieve precise spatiotemporal control and effective switching for Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) mediated chemical transformations in tumor, reducing the off-target effects. The catalytic activity of Cu catalyst through valence state interconversion between Cu(II) and Cu(I) can be precisely regulated in a reversible manner under NIR-II light irradiation-induced photoelectron transfer, which controls the extent of desired drug synthesis in bioorthogonal reaction. Meanwhile, the adverse effects of Cu(I) can be substantially mitigated within normal tissues due to their oxygen-rich condition. By utilizing NIR-II light and oxygen level, the Cu bioorthogonal catalyst achieves a balance between catalytic activity and biocompatibility. The ability to achieve precise spatiotemporal control and reversible catalysis makes this NIR-II light-mediated CuAAC platform an efficient and adaptable tool for bioorthogonal chemistry in living systems.

Preparation of M-type barium ferrite submicron absorbing powder by one-step high-temperature ball milling and its particle structure regulation

This study investigates a simple and rapid process for directly preparing M-type barium ferrite using high-temperature ball milling. By adjusting the rotation speed of the high-temperature ball milling, the morphology and size of the powder can be altered to regulate its electromagnetic properties, aiming for an overall good absorbing effect. The powder’s morphology, agglomeration properties, elemental valence states, and electromagnetic parameters were characterized using SEM, BET, XPS, EDS, and VNA. The results show that as the milling speed increases, the particle size of the M-type barium ferrite decreases, transitioning from the typical hexagonal flake particles to spherical block particles, forming a porous loose structure with richer dielectric loss mechanisms and enhanced electromagnetic wave loss capacity. Electromagnetic loss performance analysis indicates that at a milling speed of 50 rpm, the powder achieves the best electromagnetic loss of −61.16 dB at a matching thickness of 8.77 mm and a microwave absorption bandwidth of 4.1 GHz.

Redox Concomitant Formation Method for Fabrication of Cu(I)-MOF/Polymer Composites with Antifouling Properties.

Marine biofouling, which is one of the technical challenges hindering the growth of the marine economy, has been controlled using cuprous oxide (Cu2O) nanoparticles due to the exceptional antifouling properties of Cu(I) ions. However, Cu2O nanoparticles have encountered bottlenecks due to explosive releases of Cu+ ions, high toxicity at elevated doses, and long-term instability. Here, we present a novel method called Redox Concomitant Formation (RCF) for fabricating a hierarchical Cu(I) metal-organic framework polypyrrole (Cu(I)-MOF/PPy) composite. This method enables in-situ phase transition via successive redox reactions that change the chemical valence state and coordination mode of Cu(II)-MOF, resulting in a new structure of Cu(I)-MOF while creating a PPy layer surrounded by the hierarchical structure. Owing to the steady release of Cu+ ions from the Cu(I) sites and photothermal properties of PPy, Cu(I)-MOF/PPy exhibits superior and broad-spectrum resistance to marine bacteria, algae, and surface-adhered biofilms in complex biological environments, as well as long-term stability, resulting in 100% eradication efficiency under solar-driven heating. Mechanistic insights into successive structural redox reactions and formation using the RCF method are provided in detail, enabling the fabrication of novel MOFs with the desired composition and structure for a wide range of potential applications.