Ethylene dimerization is an efficient industrial chemical process to produce 1-butene, with demanding selectivity and activity requirements on new catalytic systems. Herein, a series of monodentate phosphinoamine-nickel complexes immobilized on UiO-66 are described for ethylene dimerization. These catalysts display extensive molecular tunability of the ligand similar to organometallic catalysis, while maintaining the high stability attributed to the metal-organic framework (MOF) scaffold. The highly flexible postsynthetic modification method enables this study to prepare MOFs functionalized with five different substituted phosphines and 3 N-containing ligands and identify the optimal catalyst UiO-66-L5-NiCl2 with isopropyl substituted nickel mono-phosphinoamine complex. This catalyst shows a remarkable activity and selectivity with a TOF of 29 000 (molethyl/molNi/h) and 99% selectivity for 1-butene under ethylene pressure of 15 bar. The catalyst is also applicable for continuous production in the packed column micro-reactor with a TON of 72 000 (molethyl/molNi). The mechanistic insight for the ethylene oligomerization has been examined by density functional theory (DFT) calculations. The calculated energy profiles for homogeneous complexes and truncated MOF models reveal varying rate-determining step as ß-hydrogen elimination and migratory insertion, respectively. The activation barrier of UiO-66-L5-NiCl2 is lower than other systems, possibly due to the restriction effect caused by clusters and ligands. A comprehensive analysis of the structural parameters of catalysts shows that the cone angle as steric descriptor and butene desorption energy as thermodynamic descriptor can be applied to estimate the reactivity turnover frequency (TOF) with the optimum for UiO-66-L5-NiCl2. This work represents the systematic optimization of ligand effect through combination of experimental and theoretical data and presents a proof-of-concept for ethylene dimerization catalyst through simple heterogenization of organometallic catalyst on MOF.
Currently, new clean energy storage technology must be effective, affordable, and ecologically friendly so as to meet the diverse and sustainable needs of the energy supply. In this work, NiCo-LDH containing intercalated EG was successfully prepared within 210 s using an ultrafast microwave radiation technique. Subsequently, a series of characterization and systematic electrochemical tests were conducted to analyze the composition, structure, and energy storage mechanism of the NiCo-LDH material. The Ni:Co ratio of 5:5 results in the highest capacitance value of 2156 F/g at 1 A/g and an outstanding rate performance of 86.8% capacity retention rate at 10 A/g. The results demonstrated that the unique porous structure of NiCo-LDH and large layer spacing were conducive to more electrochemical reactions. Additionally, an electrochemical test was carried out on the NiCo-LDH as a hybrid supercapacitor electrode material, with NiCo-LDH-5:5 serving as the positive electrode and activated carbon as the negative electrode, the asymmetric supercapacitor can achieve a maximum energy density of 82.5 Wh kg-1 and power density of 8000 W kg-1. The NiCo-LDH-5:5//AC hybrid supercapacitors own 81.5% cycle stability and 100% coulombic efficiency after 6000 cycles at 10 A/g.
We introduce a "solution-processing-transformation" strategy, deploying solvent vapor as scaffolds, to fabricate high-quality hydrogen-bonded organic framework (HOF) membranes. This strategy can overcome the mismatch in processing conditions and crystal growth thermodynamics faced during the facile solution processing of the membrane. The procedure includes the vapor-trigged in-situ transformation of dense amorphous supramolecules to crystalline HOF-16, with HOF-11 as the transient state. The mechanism involves a vapor-activated dissolution-precipitation equilibrium shifting and hydrogen bonding-guided molecule rearrangement, elucidated through combined experimental and theoretical analysis. Upon removal of the molecular scaffolds, the resulting HOF-16 membranes showcase significant improvement in hydrogen separation performance over their amorphous counterparts and previously reported HOF membranes. The method's broad applicability is evidenced by successfully extending it to other substrates and HOF structures. This study provides a fundamental understanding of guest-induced ordered supramolecular assembly and paves the way for the advanced manufacture of high-performance HOF membranes for gas separation processes.
Further development in the area of medicinal chemistry requires facile and atom-economical C-N bond formation from readily accessible precursors using recyclable and reusable catalysts with low process toxicity. In this work, direct N-alkylation of amines with alcohols is performed with a series of Ir-phosphine-functionalized metal-organic framework (MOF) heterogeneous catalysts. The grafted monophosphine-Ir complexes were studied comprehensively to illustrate the ligand-dependent reactivity. The afforded MOF catalysts exhibited high reactivity and selectivity toward N-alkylamine product formation, especially UiO-66-PPh2-Ir, which showed 90% conversion after recycling with no catalyst residue remaining in the product after the reaction. Furthermore, analyses of the active catalyst, mechanistic studies, control experiments, and H2 adsorption tests are consistent with the conclusion that immobilization of the iridium complex on the MOF support enables the formation of the iridium-monophosphine complex and enhances its stability during the reaction. To illustrate the potential of the catalyst for application in medicinal chemistry, two pharmaceutical precursors were synthesized with up to 99% conversion and selectivity.
As an emerging material with the potential to combine the high efficiency of homogeneous catalysts and high stability and recyclability of heterogeneous catalysts, metal-organic frameworks (MOFs) have been viewed as one of the candidates to produce catalysts of the next generation. Herein, we heterogenized the highly active mono(phosphine)-Pd complex on surface of UiO-66 MOF, as a catalyst for Suzuki and Heck cross coupling reactions. The successful immobilization of these Pd-monophosphine complexes on MOF surface to form UiO-66-PPh2-Pd was characterized and confirmed via comprehensive set of analytical methods. UiO-66-PPh2-Pd showed high activity and selectivity for both Suzuki and Heck Cross Coupling Reactions. This strategy enabled facile access to mono(phosphine) complexes which are challenging to design and require multistep synthesis in homogeneous systems, paving the way for future MOF catalysts applications by similar systems.
In this study, we employed a straightforward phosphorylation approach to achieve a dual objective: constructing c-a heterostructures consisting of crystalline Ni12P5 and amorphous FeOOH, while simultaneously enhancing oxygen vacancies. The resulting oxygen evolution reaction (OER) catalyst, Ni12P5/FeOOH/NF, exhibited remarkable performance with current densities of 500 mA cm-2 in both 1 M KOH and 1 M KOH + seawater, requiring low overpotentials of only 288 and 365 mV, respectively. Furthermore, Ni12P5/FeOOH/NF exhibited only a slight increase in overpotential, with increments of 18 mV and 70 mV in 1 M KOH after 15 and 150 h, and 32 mV and 108 mV in 1 M KOH + seawater at 500 mA cm-2 after 15 and 150 h, respectively. This minimal change can be attributed to the stabilized c-a structure, the protective coating of Ni12P5, and superhydrophilic. Through in-situ Raman and ex-situ XPS analysis, we discovered that Ni12P5/FeOOH/NF can undergo a reconfiguration into an oxygen vacancy-rich (Fe/Ni)OOH phase during OER process. The elevated OER activity is mainly due to the contribution of the oxygen vacancy-rich (Fe/Ni)OOH phase from the reconfigure of the Ni12P5/FeOOH/NF. This finding emphasizes the critical role of oxygen vacancies in facilitating the production of OO species and overcoming the limitations associated with OOH formation, ultimately enhancing the kinetics of the OER.
Adsorptive separation technology provides an effective approach for separating gases with similar physicochemical properties, such as the purification of acetylene (C2H2) from carbon dioxide (CO2). The high designability and tunability of metal-organic framework (MOF) adsorbents make them ideal design platforms for this challenging separation. Herein, we employ an isoreticular functionalization strategy to fine-tune the pore environment of Zr- and Th-based UiO-66 by the immobilization of the benzothiadiazole group via bottom-up synthesis. The functionalized UPC-120 exhibits an enhanced C2H2/CO2 separation performance, which is confirmed by adsorption isotherms, dynamic breakthrough curves, and theoretical simulations. The synergy of ligand functionalization and metal ion fine-tuning guided by isoreticular chemistry provides a new perspective for the design and development of adsorbents for challenging gas separation processes.
In this work, a series of urchin-like Ce(HCOO)3 nanoclusters were synthesized via a facile and scalable microwave-assisted method by varying the irradiation time, and the structure-property relationship was investigated. The optimization of the reaction time was performed based on structural characterizations and electrochemical performances, and the Ce(HCOO)3-210 s sample shows a specific capacitance as high as 132 F g-1 at a current density of 1 A g-1. This is due to the optimal mesoporous hierarchical structure and crystallinity that are beneficial to its conductivity, offering abundant Ce3+/Ce4+ active sites and facilitating the transportation of electrolyte ions. Moreover, an asymmetric supercapacitor based on Ce(HCOO)3//AC was fabricated, which delivers a maximum energy density of 14.78 Wh kg-1 and a considerably high power density of 15,168 W kg-1. After 10,000 continuous charge-discharge cycles at 3 A g-1, the ASC device retains 81.3% of its initial specific capacitance. The excellent comprehensive electrochemical performance of this urchin-like Ce(HCOO)3 offers significant promise for practical supercapacitor applications.
Decorating platinum (Pt) with a single atom offers a promising approach to tailoring their catalytic activity. In this study, for the first time, an innovative assistive active sites (AAS) strategy is proposed to construct high-loading (3.46wt.%) single FeâN4 as AAS, which are further hybridized with small Pt nanoparticles to enhance both oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) activities. For ORR, the target catalyst (Pt/HFeSA-HCS) exhibits a higher mass activity (MA) of 0.98 A mgPt -1 and specific activity (SA) of 1.39 mA cmPt -2 at 0.90 V versus RHE. As for MOR, Pt/HFeSA-HCS shows exceptional MA (3.21 A mgPt -1) and SA (4.27 mA cmPt -2) at peak values, surpassing commercial Pt/C by 15.3 and 11.5 times, respectively. The underlying mechanism behind this AAS strategy is to find that in MOR, FeâN4 promotes water dissociation, generating more *OH to accelerate the conversion of *CO to CO2. Meanwhile, in ORR, FeâN4 acts as a competitor to adsorb *OH, weakening PtâOH bonding and facilitating desorption of *OH on the Pt surface. Constructing AAS that can enhance dual functionality simultaneously can be seen as a successful "kill two birds with one stone" strategy.
Triplet-triplet annihilation upconversion (TTA-UC) has the potential to enhance photoredox catalysis yield. It includes a sensitizer and an annihilator. Efficient and stable annihilators are essential for photoredox catalysis, yet only a few examples are reported. Herein, we designed four novel pyrene annihilators (1, 2, 3 and 4) via introducing aryl-alkynyl groups onto pyrene to systematically modulate their singlet and triplet energies. Coupled with platinum octaethylporphyrin (PtOEP), the TTA-UC efficiency is enhanced gradually as the number of aryl-alkynyl group increases. When combining 4 with palladium tetraphenyl-tetrabenzoporphyrin (PdTPTBP), we achieved the highest red-to-green upconversion efficiency (22.4±0.3 %) (out of a 50 % maximum) so far. Then, this pair was used to activate photooxidation of aryl boronic acid under red light (630â nm), which achieved a great improved reaction yield compared to that activated by green light directly. The results not only provide a design strategy for efficient annihilators, but also show the advantage of applying TTA-UC into improving the photoredox catalysis yield.
Phosphine-functionalized metal-organic frameworks (P-MOFs) as an emerging class of coordination polymers, have provided novel opportunities for the development of heterogeneous catalysts. Yet, compared with the ubiquitous phosphine systems in homogeneous catalysis, heterogenization of phosphines in MOFs is still at its early stage. In this Minireview, we summarize the synthetic strategies, characterization and catalytic reactions based on the P-MOFs reported in literature. In particular, various catalytic reactions are discussed in detail in terms of phosphine ligand structure-function relationship, including the potential obstacles for future development. Finally, we discuss the possible solutions, including new types of reactions and techniques as the perspectives for the development of P-MOF catalysts, highlighting the opportunities and challenges.
The highly sensitive and selective detection of trace hazardous gases at room temperature is very promising for health protection and environmental safety. Herein, chemiresistive sensors for NO2 were fabricated based on self-assembled films of the four metalloporphyrin (MPor)-based metal-organic frameworks PCN-222-M (M = Cu, Ni, Co, Fe) by the quasi-Langmuir-Shäfer method. It is found that the relative responses of the four PCN-222-M films are linearly related to the NO2 concentration, and the PCN-222-Cu possessed an unprecedented high response to NO2 with a sensitivity of 2209% ppm-1 in the 4-20 ppb range and a low limit of detection (LOD) of 0.93 ppb, achieving the best performance reported so far for NO2 detection at room temperature. Meanwhile, PCN-222-Ni showed the fastest recovery among the four PCN-222-M films, which can be used for the rapid detection of NO2. Excellent reproducibility, stability, selectivity, and moisture resistance are shown for both PCN-222-Cu and PCN-222-Ni. Combining the experimental study and density functional theory (DFT) calculation, the essential roles of MPor units and the MPor/Zr6 cluster hybrid material in tuning the Fermi level and the electron transfer between PCN-222-M and NO2 were further proved. These were less considered topics in previous studies on MOFs. This work explores the application of MPor-based MOFs in gas sensing by selecting appropriate MPor units, thus providing guidance for the development of MOF-based chemiresistive sensors.
Metal-Organic Frameworks , Metalloporphyrins , Nitrogen Dioxide , Reproducibility of Results , Electron Transport , Gases , Metals
An electrode material with high performance, long durability, and low cost for supercapacitors has long been desired in academia and industry. Among all the factors that affect the electrochemical performance and cycling stability of electrode materials, the morphology and intrinsic structure characteristics are the most important. In this study, a novel 3D flower-like Ce(COOH)3 electrode material was designed by taking advantage of the Ce3+ and -COOH groups and fabricated by a one-pot microwave-assisted method. The morphology and structure characteristics of the sample were examined by SEM, EDS, TEM, XRD, FT-IR, XPS, N2 adsorption/desorption techniques, and the electrochemical behaviors were investigated in a three-electrode configuration. The Ce(COOH)3 electrode presents an excellent specific capacitance of 140 F g-1 at 1 A g-1, higher than many other previously reported Ce-based electrodes. In addition, it delivers high rate capability that retains 60% of its initial capacitance when the current density is magnified 20 times. Dramatically, the Ce(COOH)3 electrode exhibits an ultra-high cycling stability with capacitance retention of 107.9% after 60,000 cycles, which is the highest durability among reported Ce-organic compound electrodes to the best of our knowledge. The excellent electrochemical performance is ascribed to its intrinsic crystal structure and unique morphology. This work indicates that the 3D flower-like Ce(COOH)3 has significant potential for supercapacitor applications and the facile and scalable synthesis strategy can be extended to produce other metal-organic composite electrodes.
The growing global concern about environmental threats due to environmental pollution requires the development of environmentally friendly and efficient removal/detection materials and methods. Porphyrin/phthalocyanine (Por/Pc) based porous organic polymers (POPs) as a newly emerging porous material are prepared through polymerizing building blocks with different structures. Benefiting from the high porosity, adjustable pore structure, and enzyme-like activities, the Por/Pc-POPs can be the ideal platform to study the removal and detection of pollutants. However, a systematic summary of their application in environmental treatment is still lacking to date. In this review, the development of various Por/Pc-POPs for pollutant removal and detection applications over the past decade was systematically addressed for the first time to offer valuable guidance on environmental remediation through the utilization of Por/Pc-POPs. This review is divided into two sections (pollutants removal and detection) focusing on Por/Pc-POPs for organic, inorganic, and gaseous pollutants adsorption, photodegradation, and chemosensing, respectively. The related removal and sensing mechanisms are also discussed, and the methods to improve removal and detection efficiency and selectivity are also summarized. For the future practical application of Por/Pc-POPs, this review provides the emerging research directions and their application possibility and challenges in the removal and detection of pollutants.
Environmental Pollutants , Porphyrins , Environmental Pollutants/chemistry , Porosity , Polymers/chemistry
The construction of low-Pt-content intermetallic on carbon supports has been verified as a promising method to promote the activity of the oxygen reduction reaction (ORR). In this study, we have developed a simple and effective strategy to obtain a well-designed CNT-PtFe-PPy precursor. This precursor contains modulated Pt- and Fe-based content dispersed in polypyrrole (PPy) chain segments, which are in-situ generated on the templates of carbon nanotubes (CNTs). Subsequent pyrolysis of the CNT-PtFe-PPy precursor produces a CNT-PtFe@FeNC catalyst, which contains both Fe-Nx and PtFe intermetallic active sites. Due to the highly efficient dispersion of active species, the CNT-PtFe@FeNC electrocatalyst displays a 9.5 times higher specific activity (SA) and 8.5 times higher mass activity (MA) than those of a commercial Pt/C catalyst in a 0.1 M HClO4 solution. Additionally, these results, combined with excellent durability (the SA and MA maintained 94 % and 91 % of initial activity after a 10-k cycle accelerated durability test), represent among the best performance achieved so far for Pt-based ORR electrocatalysts. Furthermore, density functional theory (DFT) calculations revealed that the presence of Fe-N4 species reduces the adsorption energy between the PtFe intermetallic compound and OH*, accelerating the ORR process.
Metal-organic frameworks (MOFs) are typically assembled by bridging metal centers with organic linkers for various applications, including providing robust support for heterogeneous catalysts for CO2 reduction. In this study, we have demonstrated the solubilization of a MOF tethered to a CO2-reducing electrocatalyst and studied its fundamental electrochemistry in THF solvent using infrared spectroelectrochemistry (IR-SEC). The fundamental electrochemical properties of this immobilized catalyst were compared to that of its homogeneous counterpart. This approach provides a foundation for future experimental studies to bridge the gap between homogeneous and heterogeneous electrocatalysis.
While trinuclear [FexM3-x(µ3-O)] cluster-based metal-organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [FexM3-x(µ3-O)]-based MOFs (PCN-250, M = Ni2+, Co2+, Zn2+, Mg2+) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe3+ sites was observed along with the transformation of Fe3+ coordination geometries from octahedron to square pyramid. Furthermore, the effect of divalent metals in heterometallic PCN-250 was studied for the purpose of reducing the activation temperature and increasing the number of open metal sites. The metal site structures were corroborated by X-ray absorption and infrared spectroscopy. These results will not only guide the pretreatment of [FexM3-x(µ3-O)]-based MOFs but also corroborate spectral and computational studies on these materials.
Next-generation ultrahigh power density proton exchange membrane fuel cells rely not only on high-performance membrane electrode assembly (MEA) but also on an optimal cell structure. To this end, this work comprehensively investigates the cell performance under various structures, and it is revealed that there is unexploited performance improvement in structure design because its positive effect enhancing gas supply is often inhibited by worse proton/electron conduction. Utilizing fine channel/rib or the porous flow field is feasible to eliminate the gas diffusion layer (GDL) and hence increase the power density significantly due to the decrease of cell thickness and gas/electron transfer resistances. The cell structure combining fine channel/rib, GDL elimination and double-cell structure is believed to increase the power density from 4.4 to 6.52 kW L-1 with the existing MEA, showing nearly equal importance with the new MEA development in achieving the target of 9.0 kW L-1 .
Reducing the loading of Pt precious metal is the promising pathway to positively promote the large-scale application for fuel cells and water electrolysis. In this work, a composite bifunctional electrocatalyst (named Pt@FeSA-N-C) consisting of the atomically dispersed FeN4 active sites and Pt nanoparticles (NPs) is successfully prepared for oxygen reduction reaction (ORR) and hydrogen evolution reactions (HER). In the process of synthesizing precursor of Pt(OH)4-Fe-Ppy@CNFs, the Fe-Ppy@CNFs was firstly prepared where the highly dispersed Fe3+ ions were pre-anchored into polypyrrole (PPy) matrixes through in-situ polymerization on the surface of cellulose nanofibers (CNFs) and then Pt(OH)4 nano-particles were deposited on Fe-Ppy@CNFs through adjusting the pH of the solution by urea hydrolysis to obtain the Pt(OH)4-Fe-Ppy@CNFs. Compared with the commercial 20 wt.% Pt/C, the obtained Pt@FeSA-N-C possesses 5.5 wt.% low Pt loading. The strong synergistic effect of dual active sites between Pt NPs and FeN4 on one-dimensional (1D) FeSA-N-C support with a large surface area ensures effectively exposure of Fe and especial Pt active sites in the Pt@FeSA-N-C. Both ORR and HER activities of the Pt@FeSA-N-C were greatly improved in acid and alkaline media, even outperforming the commercial 20 wt.% Pt/C. Furthermore, the Pt@FeSA-N-C shows an unordinary stability, with no obvious decrease in the current density after 5000 and 1000 cycles of accelerated durability tests (ADTs) for ORR and HER processes, respectively. This work highlights a preparation strategy for the synergistic effect between low-loading Pt precious metal and non-precious metals in electrocatalytic system.
