Zr Sites Research Articles

In Situ FTIR Spectroscopy for Scanning Accessible Active Sites in Defect-Engineered UiO-66.

Three UiO-66 samples were prepared by solvothermal synthesis using the defect engineering approach with benzoic acid as a modulator. They were characterized by different techniques and their acidic properties were assessed by FTIR spectroscopy of adsorbed CO and CD3CN. All samples evacuated at room temperature contained bridging μ3-OH groups that interacted with both probe molecules. Evacuation at 250 °C leads to the dehydroxylation and disappearance of the μ3-OH groups. Modulator-free synthesis resulted in a material with open Zr sites. They were detected by low-temperature CO adsorption on a sample evacuated at 200 °C and by CD3CN even on a sample evacuated at RT. However, these sites were lacking in the two samples obtained with a modulator. IR and Raman spectra revealed that in these cases, the Zr4+ defect sites were saturated by benzoates, which prevented their interaction with probe molecules. Finally, the dehydroxylation of all samples produced another kind of bare Zr sites that did not interact with CO but formed complexes with acetonitrile, probably due to structural rearrangement. The results showed that FTIR spectroscopy is a powerful tool for investigating the presence and availability of acid sites in UiO-66, which is crucial for its application in adsorption and catalysis.

ZnxZrO2+x-Based Photocatalyst with Dual Active Sites for Tunable Syngas Production from CO2 Photoreduction

Photocatalytic reduction of CO2 in H2O to CO and H2 for syngas production is an attractive option to solve global warming and generate a feedstock for the Fischer–Tropsch process. The syngas generated from CO2 photoreduction with a precise and controllable ratio of H2/CO remains a major challenge to date. In this work, CdS-sensitized nanoscale ZnxZrO2+x solid solutions with dual active sites were synthesized as photocatalysts for tunable syngas H2 and CO production from CO2 photoreduction. The staggered band energy alignments, electron paramagnetic resonance results, and the site of palladium/gold nanoparticles by photodeposition indicate that the charge transfer in the CdS/ZnxZrO2+x heterojunction mainly follows the conventional type II mechanism. Density functional theoretical calculation results reveal that Zn and Zr sites on ZnxZrO2+x are favorable for the adsorption of H2O and CO2 molecules and generation of H2 and CO, respectively. The H2/CO ratio can be controlled in the range from 0.9 to 25.0 by adjusting the content of Zn in ZnxZrO2+x. Moreover, syngas production can be further improved by the modification of Pd nanoparticles. For the first time, this work proposes a strategy to construct a photocatalyst with dual active sites for effectively controlling the H2/CO ratio in syngas synthesis through a fundamental understanding of adsorption and catalytic reaction sites in both H2 evolution and CO2 reduction reactions.

MOF-derived W/Zr bimetallic oxides@Carbon for comprehensively remedying melamine foam electrode defects in vanadium redox flow batteries

Due to a series of defects such as low conductivity, poor catalytic activity and unfavorable long-term cycling stability, the comprehensive modification and usage improvement of carbonized melamine foam remain a significant challenge. Here, introducing W site into Zr-UiO-66 framework is proposed to construct W/Zr bimetallic oxides@carbon melamine foam electrode, which exhibits larger specific surface area, higher conductivity and catalytic activity than the pristine MF electrode. Benefiting from the ordered arrangement of W, Zr sites in the MOF precursor, the catalyst has an extremely catalytic activity and ultra-high binding performance of W/Zr bimetallic oxide particles with MF substrate. The electrode W/ZrBO@C-1000 possesses improved specific surface areas, hydrophilicity, higher electrochemical reactivity and reversibility compared to the pristine CMF-1000 electrode, as confirmed by material and electrochemical characterizations. The corresponding VRFB is able to achieved an energy efficiency of 82.43% at 200 mA cm−2, and displays a desirable long-term stability over 500 consecutive charge–discharge cycles. Density function theory further clarifies the underlying catalysis mechanism of bimetallic oxides for vanadium redox reactions. The strategy of introducing bimetallic oxides basing on MOF precursors improves the performance of melamine foam electrodes, which is expected to be a solution to remedy defects and broaden its usage range in other flow batteries.

Strong NiOx and ZrO2 interactions to eliminate the inhibiting effect of trace oxygen for propane dehydrogenation by accelerating lattice oxygen releasing

Recently, the ZrO2-based catalysts for PDH exhibited high activity owing to the formation of oxygen vacancy and coordinatively unsaturated Zr (Zrcu) sites. However, industrial C3H8 raw gases typically contain trace amounts of oxygen at 10–1000 ppm, which can significantly decrease the PDH activity of nano-sized ZrO2 catalyst, because that oxygen vacancy can be filled by the O2 molecules rapidly, while the rate of lattice oxygen consumption is relatively slow. Here, highly dispersed NiOx species loading on ZrO2 significantly increased C3H6 formation rate (up to 6.6 times) and decreased the activation energy. The strong interaction between NiOx species and ZrO2 enhances the ability of ZrO2 to release its lattice oxygen, and increases the concentration of oxygen vacancy and unsaturated Zr-O acid-base pairs for PDH. This strategy can expand to other metal oxides interacted with ZrO2 to eliminate the inhibiting effect of trace oxygen, such as GaOx, CoOx, CrOx, LaOx, and InOx.

Construction of electron-deficient zirconium sites for the efficient catalytic transfer hydrogenation of levulinic acid

Zirconium-derived catalyst with abundant Lewis acid-base pairs has earned it a place of prominence for the catalytic upgrade of bio-based carbonyls to valuable chemicals and fuels through catalytic transfer hydrogenation (CTH) reaction. However, the low catalytic efficiency of Zr-based catalysts urgently needs to be improved to meet the criterion for their industrial deployment. In this contribution, tungstophosphoric acid (HPW) was demonstrated as an effective modifier to the electronic structure of the pristine polyacrylonitrile and lignin-supported Zr nanofiber (Zr-Lig@PAN) to boost the CTH of levulinic acid (LA) into γ-valerolactone (GVL). Especially, an impressive GVL formation rate of 32.5 mmol·g−1·h−1 was implemented over Zr/HPW0.75g-Lig@PAN, significantly prevailing over the previous reported Zr-based catalysts for the CTH of LA or its ester to GVL. Mechanistic investigations well demonstrated that the superior electron-accept ability of HPW allowed the construction of electron-deficient Zr sites, which is beneficial to the adsorption and activation of LA and isopropanol, thus boosting the CTH reaction. These findings open up a new avenue to design efficient Zr-based catalysts for the CTH reaction by elaborately tuning the electronic structure of the catalyst in the presence of a second metal.

Dynamic Bond-Directed Synthesis of Stable Mesoporous Metal–Organic Frameworks under Room Temperature

Stable metal-organic frameworks (MOFs) with mesopores (2-50 nm) are promising platforms for immobilizing nanosized functional compounds, such as metal-oxo clusters, metal-sulfide quantum dots, and coordination complexes. However, these species easily decompose under acidic conditions or high temperatures, hindering their in situ encapsulation in stable MOFs, which are usually synthesized under harsh conditions involving excess acid modulators and high temperatures. Herein, we report a route for the room-temperature and acid-modulator-free synthesis of stable mesoporous MOFs and MOF catalysts with acid-sensitive species encapsulated: (1) we initially construct a MOF template by connecting stable Zr6 clusters with labile Cu-bipyridyl moieties; (2) Cu-bipyridyl moieties are subsequently exchanged by organic linkers to afford a stable version of Zr-MOFs; (3) acid-sensitive species, including polyoxometalates (POMs), CdSeS/ZnS quantum dots, and Cu-coordination cages, can be encapsulated in situ into the MOFs during step 1. The room-temperature synthesis allows the isolation of mesoporous MOFs with 8-connected Zr6 clusters and reo topology as kinetic products, which are inaccessible by traditional solvothermal synthesis. Furthermore, acid-sensitive species remain stable, active, and locked within the frameworks during MOF synthesis. We observed high catalytic activity for VX degradation by the POM@Zr-MOF catalysts as a result of the synergy between redox-active POMs and Lewis-acidic Zr sites. The dynamic bond-directed method will accelerate the discovery of large-pore stable MOFs and offer a mild route to avoid the decomposition of catalysts during MOF synthesis.

Understanding the Role of Synthetic Parameters in the Defect Engineering of UiO-66: A Review and Meta-analysis

UiO-66 is one of the most significant and highly studied metal–organic frameworks to date due to its exceptional thermal and chemical stability and its demonstrated potential in a myriad of applications, such as the purification of contaminated waters, gas storage, and catalysis. Defective UiO-66, where either organic linkers or whole inorganic clusters are missing from the pristine framework structure, is of key interest as the unsaturated Zr sites left by these missed connections lead to enhanced catalytic and adsorptive performance, among other benefits such as increased surface area. A solvothermal approach with the inclusion of modulators is typically employed to synthesize defective UiO-66, but a complete understanding of the links between synthetic parameters and structural outcomes has yet to be reached. This review aims to address this gap by providing a thorough overview of the current literature and a detailed discussion of key aspects of the synthesis of UiO-66 and its resulting defectivity; this literature review is supported by a meta-analysis of representative experimental papers. The focus of the meta-analysis is to draw, where possible, quantitative connections between important synthetic parameters (namely, temperature, time, modulator acidity, and reagent concentration) and the structural features reported in the literature for defective UiO-66 (namely, quantitative defectivity, defect types, surface area, particle size, and pore volume). Despite significant limitations of the meta-analysis data set, we are able to determine some statistically significant relationships between parameters and provide recommendations for essential future experimental work. The research questions not conclusively answered by the meta-analysis are addressed by a thorough examination of individual papers discussing the various influencing factors. From this, we provide recommendations to aid the judicious choice of reagents and other synthetic parameters. Overall, this detailed analysis and review compiles critical experimental findings, provides key insights into optimizing defect formation in UiO-66, and highlights important research gaps in the current literature.

Machine Learning-Aided Band Gap Engineering of BaZrS3 Chalcogenide Perovskite

The non-toxic and stable chalcogenide perovskite BaZrS3 fulfills many key optoelectronic properties for a high-efficiency photovoltaic material. It has been shown to possess a direct band gap with a large absorption coefficient and good carrier mobility values. With a reported band gap of 1.7-1.8 eV, BaZrS3 is a good candidate for tandem solar cell materials; however, its band gap is significantly larger than the optimal value for a high-efficiency single-junction solar cell (∼1.3 eV, Shockley-Queisser limit)─thus doping is required to lower the band gap. By combining first-principles calculations and machine learning algorithms, we are able to identify and predict the best dopants for the BaZrS3 perovskites for potential future photovoltaic devices with a band gap within the Shockley-Queisser limit. It is found that the Ca dopant at the Ba site or Ti dopant at the Zr site is the best candidate dopant. Based on this information, we report for the first time partial doping at the Ba site in BaZrS3 with Ca (i.e., Ba1-xCaxZrS3) and compare its photoluminescence with Ti-doped perovskites [i.e., Ba(Zr1-xTix)S3]. Synthesized (Ba,Ca)ZrS3 perovskites show a reduction in the band gap from ∼1.75 to ∼1.26 eV with <2 atom % Ca doping. Our results indicate that for the purpose of band gap tuning for photovoltaic applications, Ca-doping at the Ba-site is superior to Ti-doping at the Zr-site reported previously.

Effect of crystal structure of ZrO2 catalyst on isobutene synthesis from CO hydrogenation

ZrO2 catalysts with different crystal structures show different catalytic performance in isobutene synthesis from CO hydrogenation reaction. Although monoclinic ZrO2 has the best catalytic performance in isobutene synthesis from syngas, its isosynthesis active sites are still not well understood. To better understand the critical parameters that influence syngas to isobutene reactions over ZrO2 catalysts, we prepared a series of ZrO2 catalysts with distinct crystal structures and investigated their catalytic performance of CO hydrogenation to isobutene. Compared with tetragonal and amorphous ZrO2 catalysts, there are more coordinatively unsaturated Zr and O sites on the surface of monoclinic ZrO2 catalyst. The coordinatively unsaturated Zr sites are the active sites of CO adsorption and activation, which is beneficial to CO conversion. The coordinatively unsaturated O sites provide more basic sites for isobutene formation. Furthermore, the coordinatively unsaturated Zr and O sites on monoclinic ZrO2 catalyst surface may inhibit electron transfer to formate species formed during reaction, resulting in weak adsorption on catalyst surface of formate species. The weakly adsorbed formate species on the surface of monoclinic ZrO2 catalyst is favorable for the synthesis of isobutene from CO hydrogenation reaction.

Sb-doped β-SrZrS3 as a low-toxic and low-priced absorber for intermediate band solar cells: A first-principles investigation

Intermediate band solar cell (IBSC) has received wide attention since it is considered as a feasible approach to overcome the Shockley-Quisser limit. Here, by using the first-principles calculations with HSE06-type hybrid functional, our calculated band gap of 2.04 eV is in line with the experimental result and demonstrates that β-SrZrS3 is a suitable host for the absorber of IBSC. A separated and partially-filled intermediate band(IB) is inserted into the forbidden gap of β-SrZrS3 after Sb replacing at Zr site (SbZr). Due to the presence of the IB, three-photon absorptions can be achieved in SbZr-doped SrZrS3 and the corresponding optical absorption coefficient matches the solar light spectrum adequately. Moreover, our calculated defect formation energy of SbZr is 0.94 eV, which is lower than that of SbS or SbSr under Sr-poor, Zr-poor and S-rich condition. Finally, Sb-doped β-SrZrS3 is recommended as a prospective low-toxic and low-priced absorber for IBSC.

Steering Electron Density of Zr Sites Using Ligand Effect in Bio‐Beads for Efficient Defluoridation

AbstractBecause of spontaneous agglomeration effect and undesirable electronic state of Zr sites on the surface, zirconium (hydro)oxides generally exhibit suboptimal defluoridation capacity. Herein, a template confinement‐ligand anchoring strategy is developed by utilizing confined growth of zirconium hydroxide (ZH) inside chitosan hydrogel beads (CHB) and subsequent anchoring of fumaric acid (fm) on its surface Zr sites in a monodentate mononuclear coordination mode. This technique leads to uniform dispersion of ultrafine fmZH (≈3.4 nm) and tunable electron density at the Zr sites. Due to the electron‐withdrawing ability of fm, electron‐delocalized Zr sites increase the orbital energy level matching and vacate Zr 4d orbitals to promote hybridization with the F 2p orbitals. Ultimately, robust ZrF bond can be formed as a result of reduced the adsorption energy toward fluoride ions. The defluoridation capacity shows positive linear relationship with the electron extraction ability of ligands. The saturation adsorption capacity and dynamic treatment capacity of CHB@fmZH are 10.8 and 45.9 times higher than that of CHB@ZH, respectively, owing to high electron extraction (0.098 e−) of fm. This study offers a novel insight into the design and synthesis of high‐efficiency metal oxide adsorbents by steering its surface metal sites’ electronic state through ligand effect.

Microstructure, chemical bond characteristics, and dielectric response of Cr/Sb co-doped molybdate-based ceramics at microwave and terahertz frequency

In this research, Cr/Sb was co-doped in Ce2Zr3(MoO4)9 ceramic to optimize the microwave dielectrics and explore the intrinsic mechanism. All ceramics were synthesized using the traditional ceramic method to investigate the effects of Cr/Sb on the microstructure, chemical bond characteristics, phonon vibration spectra, and dielectric response at microwave and terahertz frequencies. X-ray diffraction analysis identified that all samples crystallized in a trigonal system, and no additional peaks observed. The dense ceramic was obtained at 875 °C based on the observed sintering behaviors. The co-addition of Cr/Sb significantly reduced the dielectric loss in the matrix. Therefore, dielectric parameters were discussed in terms of intrinsic factors. The findings of chemical bond indicate that Zr(Cr/Sb)–O bonds possess a close relationship with microwave dielectric properties, and Cr/Sb is occupied preferentially on the Zr(1) sites. Infrared spectrum analysis identified that phonon vibration lower than 400 cm−1 contribute 72.1% to the polarization. In our comparison between the infrared spectrum and terahertz time-domain (THz-TD) spectrum, we found that the permittivity extracted by the latter is closer to the observed value. Consequently, the outstanding parameters of εr = 10.53, Qf = 72,656 GHz, τf = −16.77 ppm/°C were obtained in the Ce2[Zr0.98(Cr0.5Sb0.5)0.02]3(MoO4)9 ceramic.

A REE-based zircon geothermometer based on improved lattice strain modeling of zircon-melt REE partition coefficients

Several methods for tracing geological processes based on the rare earth element (REE) concentrations in zircon have been proposed in recent years. Application of these methods requires quantitative knowledge of the partition coefficients (D) for the REE between zircon and co-existing phases, which may be melt, fluid, or other minerals. Precisely determining the DREE of zircon, however, is challenging. This is especially true for the light rare earth elements, which generally occur in very low concentrations in zircon. This difficulty can be overcome by modeling DREE using a prediction function based on the crystal lattice strain model. The prediction function is defined by three empirically derived lattice strain parameters: the apparent Young's Modulus E of the Zr site in which the REE resides; the ionic radius r0 of a (fictive) REE optimally fitting into this site; and the maximum partition coefficient D0 of this optimally fitting REE. In principle, these three parameters can be determined by fitting the prediction function to sets of measured DREE. The ionic radii of the REE, however, are all larger than r0 for zircon, commonly resulting in strain model fits yielding physically unrealistic values of r0, in particular. Here, we use a compilation of zircon-melt REE partition coefficients from the literature to establish a new empirical relationship between r0 and E, which is used as an additional constraint during lattice strain model curve fitting. Lattice strain parameters for literature DREE data sets of natural and synthetic zircon samples are calculated using our constraint resulting in a new parametrization of the inverse temperature dependence of D0. This parametrization enables quantitative estimates of REE-based crystallization temperatures of magmatic zircons, complementing estimates based on Ti-in-zircon geothermometry.

Accelerated Discovery of Novel Garnet-Type Solid-State Electrolyte Candidates via Machine Learning.

All-solid-state batteries (ASSBs) have attracted considerable attention because of their higher energy density and stability than conventional lithium-ion batteries (LIBs). For the development of promising ASSBs, solid-state electrolytes (SSEs) are essential to achieve structural integrity. Thus, in this study, a machine-learning-based surrogate model was developed to search for ideal garnet-type SSE candidates. The well-known Li7La3Zr2O12 structure was used as a base material, and 73 chemical elements were substituted on La and Zr sites, leading to 5329 potential structures. First, the elasticity database and machine learning descriptors were adopted from previous studies. Subsequently, the machine-learning-based surrogate model was applied to predict the elastic properties of potential SSE materials, followed by first-principles calculations for validation. Furthermore, the active learning process demonstrated that it can effectively decrease prediction uncertainty. Finally, the ionic conductivity of the mechanically superior materials was predicted to suggest optimal SSE candidates. Then, ab initio molecular dynamics simulations are followed for confirmation of diffusion behavior for materials classified as superionic; 10 new tetragonal-phase garnet SSEs are verified with superior mechanical and ionic conductivity properties. We believe that the current model and the constructed database will become a cornerstone for the development of next-generation SSE materials.

First principles investigations of structural and electronic properties of Ga-doped ZnZrOx solid solutions for catalytic reduction of CO2

ZnZrOx and gallium-doped ZnZrOx solid solutions exhibit excellent catalytic properties for the hydronation of CO2 to methanol. However, the details of the structures and catalytic properties are not fully understood. Herein, density functional theory has been used to explore the structural, electronic and catalytic properties of ZnZrOx and gallium-doped ZnZrOx catalysts. We used zinc-doped Zr sites of tetragonal ZrO2 with different Zn concentrations as a model to simulate the ZnZrOx solid solution. For the Ga-doped ZnZrOx catalysts, Zr atoms were substituted by Ga atoms. The doping of Zn atoms in ZrO2 reduce the coordination numbers of Zr atoms. Heavily Zn-doped ZrO2 systems do not maintain the tetragonal structure and, hence, deviate from the perfect tetragonal phase. At ∼29.16% Zn concentration, the bandgap of ZnZrOx has been reduced from 4.45 to 2.45 eV. The insertion of Ga in ZnZrOx solid solutions shifts the conduction band edges back, increasing the bandgap of the solid solutions. The Ga doping improves the CO2 adsorption ability of ZnZrOx solid solutions and efficiently dissociates the H2 molecules. On the surface of Ga-Zn doped ZrO2(101), the hydrogenation of CO2 to methanol via the formate pathway is more favorable than the CO pathway.

Entropy stabilized cubic Li7La3Zr2O12 with reduced lithium diffusion activation energy: studied using solid-state NMR spectroscopy.

Stabilizing cubic polymorph of Li7La3Zr2O12 at low temperatures is challenging and currently limited to mono- or dual-ion doping with aliovalent ions. Herein, a high-entropy strategy at the Zr sites was deployed to stabilize the cubic phase and lower the lithium diffusion activation energy, evident from the static 7Li and MAS 6Li NMR spectra.

An electrochemical impedimetric platform formed by a CNT@UiO-66 nanocomposite for quantitative analysis of oxytetracycline.

Functional materials are considered one of the most critical factors in constructing high-performance electrochemical aptasensors in the sensing field. In this work, the microporous Zr-MOF UiO-66 (UiO = Universitetet i Oslo) is selected for assembly with carbon nanotubes (CNTs) to prepare a CNT@UiO-66 composite. The as-synthesized CNT@UiO-66 composite has a high surface area, excellent stability, good electrical conductivity, and abundant Zr(IV) sites, conferring it great potential for application in fabricating high-performance electrochemical aptasensors. It is gratifying that this electrochemical impedimetric aptasensor can detect trace oxytetracycline (OTC) from 0.01 to 0.7 pg mL-1 with a low limit of detection (LOD) of 1.48 fg mL-1. Meanwhile, this fabricated sensor based on CNT@UiO-66 has fine stability, excellent selectivity, and available reproducibility. In particular, the CNT@UiO-66-based aptasensor can quantitatively detect the OTC concentration in real samples.

Coupling multifunctional catalytic active sites into metal carbide catalysts to promote the multipath bidirectional conversion of Li-S redox

Li-S batteries are hampered by sluggish liquidsolid redox and shuttle effects. Herein, a strategy of coupling multifunctional catalytic sites is proposed to fabricate bidirectional catalysts to promote multipath bidirectional Li-S redox conversion. By engineering Co or Zr dopants into Ni3C/C, the obtained Co0.30Ni2.70C/C and Zr0.30Ni2.70C/C electrocatalysts play different roles in polysulfide adsorption and multipath bidirectional conversion. During the discharging/charging process, due to limited electron transfer between the Co3+/Co2+ pair and polysulfides, Co sites themselves are catalytically inactive for the conversion of polysulfides and only act as promoters to improve the catalytic activity of Ni sites. In contrast, in addition to being promoters, Zr sites serve as electron acceptors and donors to catalyze bidirectional Li-S redox due to the flexible electron transfer between the Zr4+/Zr2+ pair and polysulfides. Such bidirectional electron transfer is accompanied by thiosulfate-mediated redox. Therefore, Zr doping not only accelerates the inherent solid (S8)-liquid (polysulfide)-solid (Li2S) conversion pathway but also propels the reversible thiosulfate-mediated conversion pathway. As a result, when the Zr0.30Ni2.70C/C nanosheets were used to modify the commercial PP separator, the Li-S batteries exhibit improved electrochemical performance (a decay of 0.0756 % over 200 cycles with a sulfur loading of 5.0 mgs cm−2).

Ru/Zr(OH)4 as a Transfer Hydrogenation Catalyst under Additives‐Free Condition

AbstractRu/Zr(OH)4 was developed as an effective transfer hydrogenation catalyst for a broad substrate scope, including nitro, alkene, and aldehyde/ketones groups without additives. XPS study and catalyst evaluation indicated that Ru0 was the main active catalytic species during the reaction. FT‐IR and CO2‐TPD analysis showed that Zr(OH)4 has abundant basic sites. The synergistic effect of Ru metal and basic sites of Zr(OH)4 support provides Ru/Zr(OH)4 with good catalytic activity without additional base addition. Ru−H− active species was detected by 1H solid‐state NMR, and the mechanism of nitrobenzene transfer hydrogenation was proposed. Ru/Zr(OH)4 catalyst was stable and can be reused for at least 5 cycles with only slight loss of activity and selectivity. This methodology provides an environmentally benign process for transfer hydrogenation under additives‐free conditions with the advantages of high activity, stability, and broad substrate scope.

Tröger's Base Chemistry in Solution and in Zr(IV)-Based Metal-Organic Frameworks.

Tröger's base (TB) and its derivatives have been studied extensively due to their unique concave shape stemming from the endomethylene strap. However, the strap-clipped TB chemistry has been largely overlooked in metal-organic framework (MOF) solids, leading to a gap in our knowledge within this field. In this work, we report the in situ strap elimination of a carboxylate-carrying TB in the presence of formic acid, both in solution and in Zr(IV)-based MOFs. In the solution system, the methanodiazocine nucleus can be exclusively transformed into an N,N'-diformyl-decorated phenhomazine derivative, regardless of the solvent used (DMF, DMA, or DEF), as unambiguously uncovered by single crystal X-ray crystallography. In contrast, while in the MOF synthetic system, the degree of derivatization reaction can be effectively controlled to give either the secondary diamine or formyl-decorated diamine, depending on the solvent used (DMF or DEF), resulting in the formation of two Zr-MOFs with 8-connected bcu (NU-1900) and 12-connected fcu (NU-407) topologies, respectively. The derivatization mechanism is proposed to be topology-guided and dependent on the local acid concentration during the MOF formation processes. Moreover, we discovered a novel post-synthetically water-induced in situ linker formylation process in NU-1900 through sequential formic acid elimination, migration, and condensation processes, affording an isostructural framework with the same linker as in NU-407, which further corroborates our proposed mechanism. Additionally, the highly defective NU-1900 with abundant accessible Zr sites was demonstrated to be an outstanding catalyst for the detoxification of a nerve agent simulant with a half-life of less than 1 min.