Studies on Transformation of Metal-Organic Frameworks for Catalysis

Schematic (top left), HR-TEM (top right) and EDS mapping (bottom) of the Ni2P NPs entrapped in mesoporous graphene via a post-transformation process. Single crystal X-ray structure of ZnCPazo-2 (a), (b) The coordination modes of the BDC2 and pyridines. c) Structure projected along the b-axis, showing non-porous framework. Note that there is no data for 2 due to the difficulty of indexing. a) CO2 adsorption/desorption isotherms obtained at 195 K.

Schematic representations of the different phase transition processes for (b) 1(Cu) and 1(Zn), and (c) 1(Co) and 1(Ni). CO2 adsorption/desorption isotherm of flexMOF(CN) and in-situ XRPD experimental results at 196 K. a) Schematic illustration of the phase transitions of flexMOF(CN) upon gas removal/reintroduction and CO2 adsorption/desorption. CO2 adsorption/desorption isotherm of flexMOF(CH2) and in-situ XRPD experimental results at 196 K. a) Schematic illustration of the phase transitions of flexMOF(OH) upon gas removal/reintroduction and adsorption/desorption of CO2 and H2O molecules .

Representation of the linear connection between nitrile-functionalized macrocyclic and BPTC ligands via coordinate and hydrogen bonds. Tabular overview of the preparation and results of flexCatal for ethylene dimerization. a) Schematic representation of mechanistic pathways for ethylene dimerization, where M = metal ions.

Development of Advanced Materials via Conversion of Metal-Organic

Porous Carbons

Meanwhile, they can act as catalysts for graphitization, which will lead to the formation of porous graphitic carbon after a post-etching process. As shown in Figure 1.2, the severe thermal treatment at 1000 qC caused severe agglomeration of Ni metals in the carbon matrix, and the subsequent etching step eventually yielded mesoporous graphene (3D mesoG). To date, much effort has been devoted to investigating the factors affecting the properties of MOF-converted carbon materials.

Several papers mentioned that the porosity of parent MOFs facilitates the generation of resultant porous carbon structures from Zn-based MOFs.8,11 Meanwhile, Kim et al. To comprehensively compare these studies, we organized the results reported by different references, including our own, to verify the correlations between the surface area of the parent MOFs and the daughter carbon (Figure 1.3a) and between the Zn/C ratio of the MOF parent and carbon surface (Figure 1.3b). This is because many variables such as framework structure and stability, ligands (as carbon source), Zn ions/clusters, porosity and synthetic conditions play a comprehensive role in determining the porosity of the resultant carbon materials.

In this context, I reported the conversion of a Zn-based non-porous CP (ZnCPazo-1) into hierarchically porous carbon with different porosity by controlling thermolytic conditions such as growth rate, reaction temperature and holding time (Figure 1.3c ). In this research, since Zn metal species can act as porogens, we controlled their aggregation rate by varying the thermal conversion conditions, thus tuning the porosity. For example, N-doped porous carbon was synthesized using IRMOF-3 composed of NH2-functionalized BDC. ligands.14 Moreover, Fu et al. synthesized P/N-co-doped porous carbon via thermolysis of UiO-66- NH2 functionalized with P-containing precursors via a post-synthetic modification.15. a) Correlation between surface area of MOF precursors and surface area of thermally converted carbon products.

Metal Phosphides Nanoparticles

I can obtain metal phosphide NPs embedded in P-doped porous carbon (PPC) such as Ni12P5@PPC and Co2P@PPC simply via thermolysis under an inert atmosphere.

Organization of PART I

Controllable-Conversion toward Porosity-Tuned N-doped Carbons

Experimental Methods
Results and Discussion
Conclusions
References

XRPD patterns of ZnCPazo-1: measured pattern of synthesized ZnCPazo-1 as well as simulated pattern from single-crystal X-ray diffraction data. The result showed 3.2% weight loss at 100 oC for a coordinating water (3.2% calculated). b) BJH pore size distribution curve. XRPD patterns of ZnCPazo-2: measured pattern of synthesized ZnCPazo-2 as well as simulated pattern from single-crystal X-ray diffraction data.

Schematic drawing of the cell structure of a seawater battery, (b) The initial charge-discharge voltage profiles of the seawater batteries with different catalysts (Pt/C, RuO2, PNC-750, PNC-850 and PNC-1000) at 0.01 mA∙cm-2 for 20 hours each step, and (c) The cycling performance of the PNC-750 sample during 20 cycles.

Hierarchically Porous Adamantane-Shaped Carbon Nanoframes

Conclusions
References
Introduction
Conclusions
References
Pore Engineering of Metal-Organic Frameworks
Tuning of the Flexible Behaviors
Organization of PART II
References

UV–vis absorption spectra of an aqueous solution of RhB (50.0 mg/L) after dye adsorption with (a) mM-NC-200 and (b) m-NC at different interval times. UV–vis absorption spectra of an aqueous solution of CR (50.0 mg/L) after dye adsorption with (a) mM-NC-200 and (b) m-NC at different interval times. UV–vis absorption spectra of an aqueous solution of CR (10.0 mg/L) after dye adsorption with (a) mM-NC-200 and (b) m-NC at different interval times.

UV-vis absorption spectra of an aqueous solution of MB (50.0 mg/L) after dye adsorption with (a) mM-NC-200 and (b) m-NC at different time intervals. UV-vis absorption spectra of an aqueous solution of MB (10.0 mg/L) after dye absorption with (a) mM-NC-200 and (b) m-NC at different time intervals. The blue arrow indicates the shift of the tip from a lower angle to a higher angle. e) Comparison of percent shrinkage in unit cell volume as estimated from powder XRD data.

View along the c-axis of the structural change of the ligand-modified MIL-88B and D as a function of the number of functional groups (X) per space. Comparison of the crystal structures of the cp and op phases, indicating (c) the gate opening and (d) breathing phenomena in CO2 adsorption.

Tuning of the Flexibility in Metal-Organic Frameworks based on Pendant Arm

Conclusions
References

CO2 adsorption/desorption isotherms for flexMOF(CN), flexMOF(OH) and flexMOF(CH2) at 196 K (left) and a schematic of their flexible CO2 adsorption behavior (right). Successive cycles of CO2 adsorption/desorption isotherms for flexMOF(CN) at 196 K. a) CO2 re-adsorption/desorption isotherm for flexMOF(CN) at 196 K after reactivation by heating under vacuum. Each macrocycle of the Ni metal center stabilizes a hydrogen bond between the carboxylate oxygen of the ligand, the hydrogen of the secondary amine in the macrocycle, and the oxygen and hydrogen of the terminal hydroxyl group.

Comparison of XRPD patterns of cp-flexMOF(OH), sample after water adsorption at 298 K and after reactivation by heating under vacuum. Comparison of XRPD patterns of cp-flexMOF(CN), sample after water adsorption at 298 K and after reactivation by heating under vacuum. Comparison of XRPD patterns of cp-flexMOF(CH2), sample after water adsorption at 298 K and after reactivation by heating under vacuum. a) Ethanol and (b) benzene vapor isotherms of flexMOF(OH) at 298 K.

Anchoring Catalytic Sites in a Tailored Metal-Organic Framework

Conclusions
References

Due to the numerous types of metal ions/clusters and organic ligands that make up MOFs, the coordination strength between these components and the thermal stability of the framework can vary widely. A summary of the crystal structure of ZnCPazo-1 and some crystallographic data are listed in Tables 2.1 and 2.2. A summary of the crystal structure of ZnCPazo-2 and some crystallographic data are listed in Tables 2.3 and 2.4.

Anode assembly was performed in a glovebox under a high-purity Ar atmosphere (O2 and H2O of < 1 ppm). The electrochemical properties of the cells were tested using a battery cycler (WBCS3000L, WonAtech) at room temperature. The relative intensity ratio of the D and G bands (ID/IG) is generally proportional to the number of defects in the graphitic carbons.

Before application, we investigated the oxygen catalytic activity of the PNCs in seawater by rotating ring disk electrode (RRDE) measurements. Here we investigated the effect of the textural properties of PNCs on the electrochemical properties (electrocatalytic activity) in seawater batteries. In Figure 3.12b, ce on the on the adsorbent (mg g-1) at equilibrium.

To explore the structural and electronic properties of Ni@mesoG and Ni2P@mesoG, Raman spectroscopy was used (Figure 4.5a). The relative intensity ratio between the D and G bands (ID/IG) is generally proportional to the number of defects in a graphitic carbon. The electrocatalytic HER activity of Ni2P@mesoG was investigated in both acidic and alkaline media using a three-electrode setup (see details of electrochemical measurements in the Experimental Methods).

The structure and morphology of the Ni2P/mesoG composite were characterized by XRPD and TEM (Figure 4.13). The reaction kinetics are investigated with the Tafel slopes, extracted from the linear part of the Tafel plots derived from the polarization curves (Figure 4.14b). The lower charge transfer resistance in Ni2P@mesoG compared to that in Ni2P/mesoG was also observed from Nyquist plots of the catalysts in the alkaline medium (Figure 4.16a).

The stable nature of Ni2P@mesoG indicates the physically protective role of the graphitic carbon layers. For the former method, target-functionalized aromatic ligands can be selected for MOF synthesis and macrocyclic metal complexes can also be the right building blocks for direct MOF synthesis.9 In the latter method, PSM is a very easy method to overcome the limitations of direct MOF synthesis. compensate. synthesis, where prefunctionalized groups are likely to participate in coordination or degradation under MOF synthesis conditions.10-. Furthermore, indexing the XRD data reveals the extent to which the framework shrank during guest removal (Figure 5.1e).

With the active Pd(II) metal ions anchored to the MOF scaffold, we anticipated the synergistic effects of the flexible system on the catalytic reaction.