Hariri R., Dehghanpour S. · Applied Organometallic Chemistry · 2021 · e6422
Open a family to keep every result attached to its sample, method and conditions.
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
PCN-222(Ni) gives the highest reported formate production among the present-work PCN-222(M) catalysts.
Caveat: GC/MS and IMS/table values differ slightly in absolute value but both rank Ni highest.
4-6 · Photocatalytic reaction over PCN-222(M); Table 1 · Figure 6; Table 1 · Linked to 3 structured results
PCN-222(Fe) retains photocatalytic activity over six 10 h recycling runs and preserves its PXRD pattern after reaction.
Caveat: Cycle values are approximate bar-chart readings; the text describes no noticeable change, though the rendered bars show a small decline from roughly 52 to 47 umol.
10 · S2.3. Characterization of catalyst · Figures S11-S12 · Linked to 4 structured results
No direct electrical transport or thermoelectric measurement is reported; transport-relevant evidence is limited to PL quenching and Mott-Schottky band analysis.
Caveat: Based on the read main text, SI text, and rendered SI pages; the paper reports no direct conductivity, mobility, Seebeck coefficient, or thermoelectric measurements.
3-5 · Characterization of catalyst; Bandgap level analysis · Figure 5; Figure 7 · Linked to 2 structured results
The metalloporphyrinic PCN-222(M) frameworks are high-surface-area mesoporous MOFs with BET areas around 2010-2030 m2 g-1 and pore volumes of 1.19-1.41 cm3 g-1.
Caveat: BET and pore-volume values come from the rendered SI Table S1; isotherm shapes are qualitative/visual in Figure S5.
6 · S2.3. Characterization of catalyst · Figure S5; Table S1 · Linked to 9 structured results
Metal centres in porphyrinic PCN-222(M) improve CO2 adsorption relative to nonmetal PCN-222.
Caveat: CO2 uptake values are reported in main text; detailed adsorption curves and Qst estimates are partly graphical.
3 · Characterization of catalyst · Figure 4 · Linked to 5 structured results
The proposed mechanism involves visible-light absorption by MTCPP linkers, electron transfer to Zr clusters, Zr(IV)/Zr(III) cycling, and reduction of CO2 to formate with TEOA as sacrificial donor.
Caveat: Mechanistic picture is proposed by authors from indirect spectroscopy, band-position and photocatalysis data rather than direct operando observation.
6-7 · Reaction mechanism and pathways of CO2 reduction · Figure 8 · Linked to 4 structured results
Lower PL intensity for PCN-222(M) versus nonmetal PCN-222 indicates faster electron transfer in the metalloporphyrinic frameworks.
Caveat: PL interpretation is qualitative; no lifetime or conductivity measurement is reported in the main text.
3-4 · Characterization of catalyst · Figure 5 · Linked to 1 structured result
Mott-Schottky slopes indicate that PCN-222(M) behaves as an n-type semiconductor.
Caveat: This is band-position/electrochemical semiconductor evidence; the paper does not report direct electrical conductivity or carrier mobility.
5 · Bandgap level analysis · Figure 7b; Figures S8b-S10b · Linked to 5 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Porphyrinic ligand controls | FeTCPP, CoTCPP, NiTCPP, CuTCPP and H2TCPPisolated porphyrinic metal centres for metallated ligands; no MOF node · tetrakis(4-carboxyphenyl)porphyrin derivatives | 0D · Model SystemMolecular ligand controls, not MOFs | 5 · Photocatalytic reaction over PCN-222(M) · Figure 6 |
| PCN-222(Co)Browse family: PCN-222 / MOF-545 | not reported; Zr6-cluster PCN-222 with CoTCPP linkerZr6 oxo clusters and Co porphyrinic metal centres · tetrakis(4-carboxyphenyl)porphyrin metallated with Co (CoTCPP / MTCPP) | 3D · Pristine3D mesoporous needle-shaped PCN-222(M) framework; PXRD confirms PCN-222(M) structure | 2-3 · Introduction; Characterization of catalyst · Figure 1; Figure 2 |
| PCN-222(Cu)Browse family: PCN-222 / MOF-545 | not reported; Zr6-cluster PCN-222 with CuTCPP linkerZr6 oxo clusters and Cu porphyrinic metal centres · tetrakis(4-carboxyphenyl)porphyrin metallated with Cu (CuTCPP / MTCPP) | 3D · Pristine3D mesoporous needle-shaped PCN-222(M) framework; PXRD confirms PCN-222(M) structure | 2-3 · Introduction; Characterization of catalyst · Figure 1; Figure 2 |
| PCN-222(Fe)Browse family: PCN-222 / MOF-545 | not reported; Zr6-cluster PCN-222 with FeTCPP linkerZr6 oxo clusters and Fe porphyrinic metal centres · tetrakis(4-carboxyphenyl)porphyrin metallated with Fe (FeTCPP / MTCPP) | 3D · Pristine3D mesoporous needle-shaped PCN-222(M) framework; PXRD confirms PCN-222(M) structure | 2-3 · Introduction; Characterization of catalyst · Figure 1; Figure 2 |
| PCN-222(Ni)Browse family: PCN-222 / MOF-545 | not reported; Zr6-cluster PCN-222 with NiTCPP linkerZr6 oxo clusters and Ni porphyrinic metal centres · tetrakis(4-carboxyphenyl)porphyrin metallated with Ni (NiTCPP / MTCPP) | 3D · Pristine3D mesoporous needle-shaped PCN-222(M) framework; PXRD confirms PCN-222(M) structure | 2-3 · Introduction; Characterization of catalyst · Figure 1; Figure 2 |
| PCN-222 (no metal)Browse family: PCN-222 / MOF-545 | not reported; Zr6-cluster porphyrinic PCN-222 without porphyrinic metalZr6 oxo clusters; no porphyrinic metal centre · free-base tetrakis(4-carboxyphenyl)porphyrin (H2TCPP) | 3D · PristinePorphyrinic PCN-222 control framework | 2 · Photocatalytic reaction · Figure 6; Table 1 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| FeTCPP, CoTCPP, NiTCPP, CuTCPP and H2TCPP ligand controlsresearch_0540__mat__mat_ligand_controls | Unknown · Model System · Model | molecular controls in photocatalytic reaction | 5 · Photocatalytic reaction over PCN-222(M) · Figure 6 |
| negative photocatalysis controls: no TEOA, no CO2, and no PCN-222research_0540__mat__mat_pcn222_no_metal | Unknown · Paper Level Unspecified · Unknown | photocatalytic control experiments | 5 · Photocatalytic reaction over PCN-222(M) · Figure 6 |
| PCN-222(Co)-modified GCEresearch_0540__mat__mat_pcn222_co | Electrode · Target Sample · Composite | MOF dispersed in water and drop-cast twice onto polished GCE, dried at room temperature for 30 min after each loadingglassy carbon electrode | S2.4. Electrochemical charactirization |
| PCN-222(Co)research_0540__mat__mat_pcn222_co | Powder · Target Sample · Mixed Metal | as-prepared needle-like mesoporous crystals/powder | 2-4 · Introduction; Characterization of catalyst · Figure 3b |
| PCN-222(Cu)-modified GCEresearch_0540__mat__mat_pcn222_cu | Electrode · Target Sample · Composite | MOF dispersed in water and drop-cast twice onto polished GCE, dried at room temperature for 30 min after each loadingglassy carbon electrode | S2.4. Electrochemical charactirization |
| PCN-222(Cu)research_0540__mat__mat_pcn222_cu | Powder · Target Sample · Mixed Metal | as-prepared needle-like mesoporous crystals/powder | 2-4 · Introduction; Characterization of catalyst · Figure 3d |
| PCN-222(Fe)-modified GCEresearch_0540__mat__mat_pcn222_fe | Electrode · Target Sample · Composite | MOF dispersed in water and drop-cast twice onto polished GCE, dried at room temperature for 30 min after each loadingglassy carbon electrode | S2.4. Electrochemical charactirization |
| PCN-222(Fe)research_0540__mat__mat_pcn222_fe | Powder · Target Sample · Mixed Metal | as-prepared needle-like mesoporous crystals/powder | 2-4 · Introduction; Characterization of catalyst · Figure 3a |
| PCN-222(Ni)-modified GCEresearch_0540__mat__mat_pcn222_ni | Electrode · Target Sample · Composite | MOF dispersed in water and drop-cast twice onto polished GCE, dried at room temperature for 30 min after each loadingglassy carbon electrode | S2.4. Electrochemical charactirization |
| PCN-222(Ni)research_0540__mat__mat_pcn222_ni | Powder · Target Sample · Mixed Metal | as-prepared needle-like mesoporous crystals/powder | 2-4 · Introduction; Characterization of catalyst · Figure 3c |
| PCN-222 (no metal)research_0540__mat__mat_pcn222_no_metal | Powder · Pristine Control · Pristine Framework | prepared and tested under same optimised photocatalysis conditions | 2 · Photocatalytic reaction · Figure 6e; Table 1 |