Isoreticular Metal-organic Frameworks Research Articles

Highly Stable MOF-Type Lead Halide Luminescent Ferroelectrics.

Lead halide molecular ferroelectrics represent an important class of luminescent ferroelectrics, distinguished by their high chemical and structural tunability, excellent processability and distinctive luminescent characteristics. However, their inherent instability, prone to decomposition upon exposure to moisture and light, hinders their broader ferroelectric applications. Herein, for the first time, we present a series of isoreticular metal-organic framework (MOF)-type lead halide luminescent ferroelectrics, demonstrating exceptional robustness under ambient conditions for at least 15 months and even when subjected to aqueous boiling conditions. Unlike conventional metal-oxo secondary building units (SBUs) in MOFs adopting highly centrosymmetric structure with limited structural distortion, our lead halide-based MOFs occupy structurally deformable [Pb2X]+ (X=Cl-/Br-/I-) SBUs that facilitate a c-axis-biased displacement of Pb2+ centers and substantially contribute to thermoinducible structural transformation. Importantly, this class of MOF-type lead halide ferroelectrics undergo ferroelectric-to-paraelectric phase transitions with remarkably high Curie temperature of up to 505 K, superior to most of molecular ferroelectrics. Moreover, the covalent bonding between phosphorescent organic component and the light-harvesting inorganic component achieves efficient spin-orbit coupling and intersystem crossing, resulting in long-lived afterglow emission. The compelling combination of high stability, ferroelectricity and afterglow emission exhibited by lead halide MOFs opens up many potential opportunities in energy-conversion applications.

Avoiding pitfalls in molecular simulation of vapor sorption: Example of propane and isobutane in metal-organic frameworks for adsorption cooling applications.

This study introduces recommendations for conducting molecular simulations of vapor adsorption, with an emphasis on enhancing the accuracy, reproducibility, and comparability of results. The first aspect we address is consistency in the implementation of some details of typical molecular models, including tail corrections and cutoff distances, due to their significant influence on generated data. We highlight the importance of explicitly calculating the saturation pressures at relevant temperatures using methods such as Gibbs ensemble Monte Carlo simulations and illustrate some pitfalls in extrapolating saturation pressures using this method. For grand canonical Monte Carlo (GCMC) simulations, the input fugacity is usually calculated using an equation of state, which often requires the critical parameters of the fluid. We show the importance of using critical parameters derived from the simulation with the same model to ensure internal consistency between the simulated explicit adsorbate phase and the implicit bulk phase in GCMC. We show the advantages of presenting isotherms on a relative pressure scale to facilitate easier comparison among models and with experiment. Extending these guidelines to a practical case study, we evaluate the performance of various isoreticular metal-organic frameworks (MOFs) in adsorption cooling applications. This includes examining the advantages of using propane and isobutane as working fluids and identifying MOFs with a superior performance.

Auxiliary ligand influence on interpenetration and C2H2/CO2 separation in NDI based isoreticular MOFs

Selective separation of C2H2 from CO2 mixtures promises a critical industrial process to produce high-purity C2H2 but challenging due to their similar physical properties and molecular sizes/shapes. Naphthalenediimide (NDI) ligand-based metal − organic frameworks (MOFs) exhibit potential in selective adsorption of C2H2 due to NDI’s high affinity to C2H2 molecules. Here, three iso-reticular NDI based MOFs (denoted as FJU-109, 110 and 111) are obtained by tuning interpenetration using auxiliary ligands of different lengths. Based on the actual column breakthrough experiments, FJU-111 can achieve separation C2H2/CO2 mixture, with a separation selective of 2.2. Calculation of the binding energy shows that C-H…O interactions between guest and O atom from NDI ligand play a dominant role in elective recognition of acetylene.

Adsorption and Diffusion Properties of Functionalized MOFs for CO2 Capture: A Combination of Molecular Dynamics Simulation and Density Functional Theory Calculation.

The capture of carbon dioxide (CO2) from fuel gases is a significant method to solve the global warming problem. Metal-organic frameworks (MOFs) are considered to be promising porous materials and have shown great potential for CO2 adsorption and separation applications. However, the adsorption and diffusion mechanisms of CO2 in functionalized MOFs from the perspective of binding energies are still not clear. Actually, the adsorption and diffusion mechanisms can be revealed more intuitively by the binding energies of CO2 with the functionalized MOFs. In this work, a combination of molecular dynamics simulation and density functional theory calculation was performed to study CO2 adsorption and diffusion mechanisms in five different functionalized isoreticular MOFs (IRMOF-1 through -5), considering the influence of functionalized linkers on the adsorption capacity of functionalized MOFs. The results show that the CO2 uptake is determined by two elements: the binding energy and porosity of MOFs. The porosity of the MOFs plays a dominant role in IRMOF-5, resulting in the lowest level of CO2 uptake. The potential of mean force (PMF) of CO2 is strongest at the CO2/functionalized MOFs interface, which is consistent with the maximum CO2 density distribution at the interface. IRMOF-3 with the functionalized linker -NH2 shows the highest CO2 uptake due to the higher porosity and binding energy. Although IRMOF-5 with the functionalized linker -OC5H11 exhibits the lowest diffusivity of CO2 and the highest binding energy, it shows the lowest CO2 uptake. Accordingly, among the five simulated functionalized MOFs, IRMOF-3 is an excellent CO2 adsorbent and IRMOF-5 can be used to separate CO2 from other gases, which will be helpful for the designing of CO2 capture devices. This work will contribute to the design and screening of materials for CO2 adsorption and separation in practical applications.

Fine-tuning the pore environment of isoreticular metal-organic frameworks through installing functional sites for boosting C2H6/C2H4 separation

Herein, we presented a strategy that tuning the pore environment via installing functional sites in the pores to boost C2H6/C2H4 separation performance of MOFs. To prove this strategy, four isoreticular MOFs [MAF-X10, -X10(Me), -X10(Cl), and -X10(F)] were designed and synthesized based on reticular chemistry principle, which featured the regulated pore environment and exhibited intriguing differences in C2H6 and C2H4 uptakes. Methyl group-modified nonpolar pores endow these MOFs with impressive C2H6-selective behavior and high C2H6 loadings (>110 cm3 g−1), in which MAF-X10(F) with polar F sites exhibited the highest C2H6 uptake (140.5 cm3 g−1) among four MOFs, ranking the top compared to the reported MOF materials. The polar sites-functionalized MAF-X10(Cl) and -X10(F) showed the significantly improved C2H6/C2H4 separation performances in comprehensive of selectivity, separation potential, C2H4 productivity, which were mainly contributed to the strong C-H⋯Cl/F interactions formed between the active sites (Cl or F) in MAF-X10(Cl)/(F) and C2H6, as revealed by molecular simulations.

Efficient CO2 Capture and Separation in MOFs: Effect from Isoreticular Double Interpenetration.

Severe CO2 emissions has posed an increasingly alarming threat, motivating the development of efficient CO2 capture materials, one of the key parts of carbon capture, utilization, and storage (CCUS). In this study, a series of metal-organic frameworks (MOFs) named Sc-X (X = S, M, L) were constructed inspired by recorded MOFs, Zn-BPZ-SA and MFU-4l-Li. The corresponding isoreticular double-interpenetrating MOFs (Sc-X-IDI) were subsequently constructed via the introduction of isoreticular double interpenetration. Grand canonical Monte Carlo (GCMC) simulations were adopted at 298 K and 0.1-1.0 bar to comprehensively evaluate the CO2 capture and separation performances in Sc-X and Sc-X-IDI, with gas distribution, isothermal adsorption heat (Qst), and van der Waals (vdW)/Coulomb interactions. It is showed that isoreticular double interpenetration significantly improved the interactions between adsorbed gases and frameworks by precisely modulating pore sizes, particularly observed in Sc-M and Sc-M-IDI. Specifically, the Qst and Coulomb interactions exhibited a substantial increase, rising from 28.38 and 22.19 kJ mol-1 in Sc-M to 43.52 and 38.04 kJ mol-1 in Sc-M-IDI, respectively, at 298 K and 1.0 bar. Besides, the selectivity of CO2 over CH4/N2 was enhanced from 55.36/107.28 in Sc-M to 3308.61/7021.48 in Sc-M-IDI. However, the CO2 capture capacity is significantly influenced by the pore size. Sc-M, with a favorable pore size, exhibits the highest capture capacity of 15.86 mmol g-1 at 298 K and 1.0 bar. This study elucidated the impact of isoreticular double interpenetration on the CO2 capture performance in MOFs.

Reversible Postsynthetic Modification in a Metal–Organic Framework

AbstractPostsynthetic modification (PSM) of metal–organic frameworks (MOFs) provides access to functional materials and advanced porous solid engineering. Herein, we report the reversible PSM of a multivariate isoreticular MOF by applying dynamic furan‐maleimide Diels–Alder (DA) chemistry. The key step involves incorporating a furan group into the MOF via “click” PSM, which can then undergo repeated cycles of modification and de‐modification with maleimides. The structural integrity, crystallinity, and porosity of the furan‐appended MOF remained intact even after three consecutive PSM/de‐modification cycles using three different functionalized maleimides.

Reversible Postsynthetic Modification in a Metal-Organic Framework.

Postsynthetic modification (PSM) of metal-organic frameworks (MOFs) provides access to functional materials and advanced porous solid engineering. Herein, we report the reversible PSM of a multivariate isoreticular MOF by applying dynamic furan-maleimide Diels-Alder (DA) chemistry. The key step involves incorporating a furan group into the MOF via "click" PSM, which can then undergo repeated cycles of modification and de-modification with maleimides. The structural integrity, crystallinity, and porosity of the furan-appended MOF remained intact even after three consecutive PSM/de-modification cycles using three different functionalized maleimides.

Harvesting Water from Air with High-Capacity, Stable Furan-Based Metal-Organic Frameworks.

We synthesized two isoreticular furan-based metal-organic frameworks (MOFs), MOF-LA2-1(furan) and MOF-LA2-2(furan) with rod-like secondary building units (SBUs) featuring 1D channels, as sorbents for atmospheric water harvesting (LA = long arm). These aluminum-based MOFs demonstrated a combination of high water uptake and stability, exhibiting working capacities of 0.41 and 0.48 gwater/gMOF (under isobaric conditions of 1.70 kPa), respectively. Remarkably, both MOFs showed a negligible loss in water uptake after 165 adsorption-desorption cycles. These working capacities rival that of MOF-LA2-1(pyrazole), which has a working capacity of 0.55 gwater/gMOF. The current MOFs stand out for their high water stability, as evidenced by 165 cycles of water uptake and release. MOF-LA2-2(furan) is the first aluminum MOF to employ a double 'long arm' extension strategy, which is confirmed through single-crystal X-ray diffraction (SCXRD). The MOFs were synthesized by using a straightforward synthesis route. This study offers valuable insights into the design of durable, water-stable MOFs and underscores their potential for efficient water harvesting.

Two highly stable isoreticular M8-pyrazolate (M = Co, Ni) metal-organic frameworks for CO2 conversion.

Two isoreticular metal-organic frameworks (MOFs) constructed from M8(OH)4(H2O)2(pyz)12 (M = Co, Ni; pyz = pyrazolate) secondary building units (SBUs) and Ni(salen)-derived metalloligands were synthesized. The two MOFs were found to be highly stable in a wide pH and temperature range. Together with the tetrabutylammonium bromide (TBAB) co-catalyst, they catalysed the cycloaddition of CO2 to epoxides with near-quantitative yields and easy recyclability for at least 11 cycles.

Increased CO2/N2 selectivity by stepwise fluorination in isoreticular ultramicroporous metal–organic frameworks

A series of isoreticular ultramicroporous fluorinated MOFs were synthesized. Both experimental and simulation studies showed that increasing the fluorine content leads to a marked increase in CO2/N2 selectivity owing to the CF⋯C(CO2) interactions.

Quasi-Discrete Pore Engineering via Ligand Racemization in Metal-Organic Frameworks for Thermodynamic-Kinetic Synergistic Separation of Propylene and Propane.

The adsorptive separation of propylene and propane offers an energy-efficient alternative to the conventional cryogenic distillation technology. However, developing porous adsorbents with both high equilibrium and kinetic selectivity remains extremely challenging due to the similar size and physical properties of these gases. Herein, this work reports a ligand racemization strategy to construct quasi-discrete pores in MOFs for a synergistically enhanced thermodynamic and kinetic separation performance. The use of enantiopure l-malic acid versus racemic dl-malic acid as ligands afforded isoreticular Ni-based MOFs with contrasting one-dimensional channels (l-mal-MOF) and quasi-discrete cavities connected by small windows (dl-mal-MOF). The periodic pore constrictions in dl-mal-MOF significantly increased the differentiation in diffusion rates and binding energies between propylene and propane. dl-mal-MOF exhibited an exceptional propylene uptake of 1.82 mmol/g at 0.05 bar and 298 K along with an ultrahigh equilibrium-kinetic combined selectivity of 62.6. DFT calculations and MD simulations provided insights into the synergistic mechanism of preferential propylene adsorption and diffusion. Breakthrough column experiments demonstrated the excellent separation and high-purity recovery of propylene over propane on dl-mal-MOF. The robust stability and facile regeneration highlight its potential for propylene purification applications.

Effect of Ligand Aromaticity on Cyclohexane and Benzene Sorption in IRMOFs: A Computational Study.

A series of four isoreticular MOFs (IRMOF-1, -10, -14, and -16) were selected for a computational investigation of the effect of ligand aromaticity on the adsorption capacity of an aromatic VOC (benzene) compared to its nonaromatic analog (cyclohexane). The affinity of the adsorbates was evaluated by calculating Henry's constants and adsorption enthalpies. It has been evidenced that while KH values decrease with ligand elongation (IRMOF-10 and -16), inserting a pyrene core into the MOF structure (IRMOF-14) increases both the cyclohexane and benzene adsorption efficiency by ∼290 and 54%, respectively. To elucidate host-guest interactions, we sought to locate preferential adsorption sites in MOF structures for the two VOCs studied by using the GCMC method. It appears that benzene interacts with the metal center (Zn4O clusters) and most of the ligand while cyclohexane tends to localize preferentially only near the Zn4O clusters. Coadsorption isotherms (equimolar mixture of benzene and cyclohexane) demonstrated the preferential adsorption of cyclohexane due to the stronger affinity for the MOF structure. On the other hand, for other isoreticular structures, the ligand elongation leads to a shift of the adsorption curve of cyclohexane caused by pore size increase and therefore less interactions with the walls. This phenomenon is counterbalanced in the case of IRMOF-14 due to stronger interactions between the cyclohexane and pyrene groups. The present results thus open perspectives in the design of promising MOF candidates for high-performing separation and sorption/detection of hydrocarbon VOCs.

Shaping the Water-Harvesting Behavior of Metal-Organic Frameworks Aided by Fine-Tuned GPT Models.

We construct a data set of metal-organic framework (MOF) linkers and employ a fine-tuned GPT assistant to propose MOF linker designs by mutating and modifying the existing linker structures. This strategy allows the GPT model to learn the intricate language of chemistry in molecular representations, thereby achieving an enhanced accuracy in generating linker structures compared with its base models. Aiming to highlight the significance of linker design strategies in advancing the discovery of water-harvesting MOFs, we conducted a systematic MOF variant expansion upon state-of-the-art MOF-303 utilizing a multidimensional approach that integrates linker extension with multivariate tuning strategies. We synthesized a series of isoreticular aluminum MOFs, termed Long-Arm MOFs (LAMOF-1 to LAMOF-10), featuring linkers that bear various combinations of heteroatoms in their five-membered ring moiety, replacing pyrazole with either thiophene, furan, or thiazole rings or a combination of two. Beyond their consistent and robust architecture, as demonstrated by permanent porosity and thermal stability, the LAMOF series offers a generalizable synthesis strategy. Importantly, these 10 LAMOFs establish new benchmarks for water uptake (up to 0.64 g g-1) and operational humidity ranges (between 13 and 53%), thereby expanding the diversity of water-harvesting MOFs.

Isoreticular Metal-Organic Frameworks Confined Mononuclear Ru-Hydrides Enable Highly Efficient Shape-Selective Hydrogenolysis of Polyolefins.

Upcycling nonbiodegradable plastics such as polyolefins is paramount due to their ever-increasing demand and landfills after usage. Catalytic hydrogenolysis is highly appealing to convert polyolefins into targeted value-added products under mild reaction conditions compared with other methods, such as high-temperature incineration and pyrolysis. We have developed three isoreticular zirconium UiO-metal-organic frameworks (UiO-MOFs) node-supported ruthenium dihydrides (UiO-RuH2), which are efficient heterogeneous catalysts for hydrogenolysis of polyethylene at 200 °C, affording liquid hydrocarbons with a narrow distribution and excellent selectivity via shape-selective catalysis. UiO-66-RuH2 catalyzed hydrogenolysis of single-use low-density polyethylene (LDPE) produced a C12 centered narrow bell-shaped distribution of C8-C16 alkanes in >80% yield and 90% selectivity in the liquid phase. By tuning the pore sizes of the isoreticular UiO-RuH2 MOF catalysts, the distribution of the products could be systematically altered, affording different fuel-grade liquid hydrocarbons from LDPE in high yields. Our spectroscopic and theoretical studies and control experiments reveal that UiO-RuH2 catalysts enable highly efficient upcycling of plastic wastes under mild conditions owing to their unique combination of coordinatively unsaturated single-site Ru-active sites, uniform and tunable pores, well-defined porous structure, and superior stability. The kinetics and theoretical calculations also identify the C-C bond scission involving β-alkyl transfer as the turnover-limiting step.

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.

Storage and Diffusion of Carbon Dioxide in the Metal Organic Framework MOF-5─A Semi-empirical Molecular Dynamics Study.

Metal-organic frameworks (MOFs) have attracted increasing attention due to their high porosity for exceptional gas storage applications. MOF-5 belongs to the family of isoreticular MOFs (IRMOFs) and consists of Zn4O6+ clusters linked by 1,4-benzenedicarboxylate. Due to the large number of atoms in the unit cell, molecular dynamics simulation based on density functional theory has proved to be too demanding, while force field models are often inadequate to model complex host-guest interactions. To overcome this limitation, an alternative semi-empirical approach using a set of approximations and extensive parametrization of interactions called density functional tight binding (DFTB) was applied in this work to study CO2 in the MOF-5 host. Calculations of pristine MOF-5 yield very good agreement with experimental data in terms of X-ray diffraction patterns as well as mechanical properties, such as the negative thermal expansion coefficient and the bulk modulus. In addition, different loadings of CO2 were introduced, and the associated self-diffusion coefficients and activation energies were investigated. The results show very good agreement with those of other experimental and theoretical investigations. This study provides detailed insights into the capability of semi-empirical DFTB-based molecular dynamics simulations of these challenging guest@host systems. Based on the comparison of the guest-guest pair distributions observed inside the MOF host and the corresponding gas-phase reference, a liquid-like structure of CO2 can be deduced upon storage in the host material.

Electrochromism in Isoreticular Metal-Organic Framework Thin Films with Record High Coloration Efficiency.

The power of isoreticular chemistry has been widely exploited to engineer metal-organic frameworks (MOFs) with fascinating molecular sieving and storage properties but is underexplored for designing MOFs with tunable optoelectronic properties. Herein, three dipyrazole-terminated XDIs (X = PM (pyromellitic), N (naphthalene), or P (perylene); DI = diimide) with different lengths and electronic properties are prepared and employed as linkers for the construction of an isoreticular series of Zn-XDI MOFs with distinct electrochromism. The MOFs are grown on fluorine-doped tin oxide (FTO) as high-quality crystalline thin films and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Due to the constituting electronically isolated XDI linkers, each member of the isoreticular thin film series exhibits two reversible one-electron redox events, each at a distinct electrochemical potential. The orientation of the MOFs as thin films as well as their isoreticular nature results in identical cation-coupled electron hopping transport rates in all three materials, as demonstrated by comparable apparent electron diffusion coefficients, Deapp. Upon electrochemical reduction to either the [XDI]•- or [XDI]2- state, each MOF undergoes characteristic changes in its optical properties as a function of linker length and redox state of the linker. Operando spectroelectrochemistry measurements reveal that Zn-PDI@FTO (PDI = perylene diimide) thin films exhibit a record high coloration efficiency of 941 cm2 C-1 at 746 nm, which is attributed to the maximized Faradaic transformations at each electronically isolated PDI unit. The electrochromic response of the thin film is retained to more than 99% over 100 reduction-oxidation cycles, demonstrating the applicability of the presented materials.

Face-directed assembly of tailored isoreticular MOFs using centring structure-directing agents

Building blocks with low connectivity and no embedded directionality are prone to polymorphism, as demonstrated by the diversity of 4-connected zeolitic nets (>250). As a result, their deployment for design in reticular and isoreticular chemistries remains a challenge. However, the ability to control geometrical peculiarities offers potential to deviate from the assembly of default structures. Here we report the face-directed assembly of >20 isoreticular zeolite-like metal–organic frameworks (ZMOFs) by using polytopic expanding and tightening centring structure-directing agents (cSDAs). The cSDAs are selected with the appropriate geometrical coding information to alter and control the orientation of adjacent supermolecular building blocks. The ZMOFs have an underlying sodalite (sod) topology that is remarkably suited for the rational assembly of multinary materials. In addition to a variety of metal cations (In, Fe, Co and Ni), a diverse range of cSDAs (di-, tri-, tetra-, hexa-, pyridyl or imidazole) are used and combined. Our approach enables isoreticular possibilities at both extremities of the porous materials spectrum: In-sod-ZMOF-102 exhibits small pore aperture suitable for efficient separation, while Fe-sod-ZMOF-320 with 48-Å-wide mesopores exhibits high hydrogen uptake, methane storage working capacity and a high gravimetric working capacity for oxygen.

Role of Transition Metals in Metal-Organic Frameworks as Nanoporous Ion Emitters for Thermal Ionization Mass Spectrometry.

Thermal ionization mass spectrometry is a powerful analytical technique that allows for precise determination of isotopic ratios. Analysis of low abundance samples, however, can be limited by the ionization efficiency. Following an investigation into a new type of metal-organic hybrid material, nanoporous ion emitters (nano-PIEs), devised to promote the emission of analyte ions and reduce traditional sample loading challenges, this work evaluates the impact that changing the metal in the material has on the ionization of uranium (U). Being derived from metal-organic frameworks (MOFs), nano-PIEs inherit the tunability of their parent MOFs. The MOF-74 series has been well studied for probing the impact various framework metals (i.e., Mg, Mn, Co, Ni, Cu, Zn, and Cd) have on material properties, and thus, a series of nano-PIEs with different metals were derived from this isoreticular MOF series. Trends in ionization efficiency were studied as a function of ionization potential, volatility, and work function of the framework metals to gain a better understanding of the mechanism of analyte ionization. This study finds a correlation between the analyte ionization efficiency and nano-PIE framework metal volatility that is attributed to its tunable thermal stability and degradation behavior.