Li Z., Jia J., Sang Z. et al. · Angewandte Chemie - International Edition · 2024 · e202408500
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.
Ni-TCPP(Co) is the best-performing M2-TCPP(Co) analogue for alkaline 2e-ORR, with 96.5% H2O2 selectivity and 18.2 mol g-1 h-1 flow-cell yield in 1 M KOH.
Caveat: Electrochemical electrodes include CNT/Nafion processing layers.
5-6 · Catalytic Performance · Figures 3-4 · Linked to 3 structured results
Ni-TCPP(Co) remains highly selective in neutral saline/sulfate electrolytes and reaches high H2O2 concentration in 1 M NaCl flow-cell testing.
Caveat: Neutral flow-cell results are from composite GDL electrodes.
6 · Catalytic Performance · Figure 4e-f · Linked to 4 structured results
Acidic 2e-ORR performance is caveated because Ni2O8 nodes may not remain stable in acidic electrolyte, so activity may mainly come from Co-N4 sites.
Caveat: Source authors explicitly caution about acidic stability.
S28/S31 · Figure S25/S32 notes · Figure S25; Figure S32 · Linked to 2 structured results
The framework synthesis is mostly explicit, but PVP is stated in the main text as present during hydrothermal preparation while the SI recipe does not quantify or time its addition.
Caveat: Routes marked partial for this reason.
3 · Morphological and Structural Characterization
Ni-TCPP(Co) contains independent CoN4 and Ni2O8/Ni-O4 sites separated by about 1.19 nm, enabling both site density and intrinsic 2e-ORR activity.
Caveat: Independence inferred from DFT/electron-transfer analysis and spectroscopy; not a direct operando structural separation measurement.
3 · DFT Screening · Figure 1; Figure 2 · Linked to 4 structured results
TCPP-based c-MOF analogues are argued to have intrinsic metallic/high-conductivity electronic structure from PDOS crossing the Fermi level, but no direct experimental conductivity value is reported for Ni-TCPP(Co).
Caveat: Computational PDOS evidence only; no four-probe or EIS conductivity measurement extracted.
3 · DFT Screening · Figure 1e; Figure S4 · Linked to 1 structured result
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Co-TCPP(Co) | M2-TCPP(Co), M2 = CoCoN4 centres plus Co-O8 nodes · TCPP | 2D · PristineTCPP-based 2D layered c-MOF analogue | 2-3 · Results and Discussion · Figure 1 |
| Cu-TCPP(Co) | M2-TCPP(Co), M2 = CuCoN4 centres plus Cu-O8 nodes · TCPP | 2D · PristineTCPP-based 2D layered c-MOF analogue | 2-3 · Results and Discussion · Figure 1 |
| Fe-TCPP(Co) | M2-TCPP(Co), M2 = FeCoN4 centres plus Fe-O8 nodes · TCPP | 2D · PristineTCPP-based 2D layered c-MOF analogue | 2-3 · Results and Discussion · Figure 1 |
| M2-TCPP(Co) computational supercell models | M2-TCPP(Co), M2 = Mn, Fe, Co, Ni, CuCoN4 site A plus M2-O8 site B · TCPP | 2D · Model System2x2x1 supercell computational model | 3 · DFT Screening · Figure 1a |
| Mn-TCPP(Co) | M2-TCPP(Co), M2 = MnCoN4 centres plus Mn-O8 nodes · TCPP | 2D · PristineTCPP-based 2D layered c-MOF analogue | 2-3 · Results and Discussion · Figure 1 |
| Ni-TCPP(Co) | not given; TCPP(Co) linked by Ni2O8/Ni-O4 nodesCoN4 porphyrinic centres plus Ni2O8 / Ni-O4 carboxylate nodes · Tetrakis(4-carboxyphenyl)porphyrin (TCPP) | 2D · PristineTCPP-based two-dimensional layered conductive MOF nanosheets | 2-3 · Results and Discussion · Figure 1; Figure 2 |
| Ni-TCPP(Cu) | Ni-TCPP(M1), M1 = CuCuN4 porphyrinic centres plus Ni2O8 nodes · TCPP | 2D · PristineTCPP-based 2D c-MOF analogue | S5 · Experimental section |
| Ni-TCPP(Mn) | Ni-TCPP(M1), M1 = MnMnN4 porphyrinic centres plus Ni2O8 nodes · TCPP | 2D · PristineTCPP-based 2D c-MOF analogue | S5 · Experimental section |
| TCPP(M1) computational monomer models | TCPP(M1), M1 = Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt, Ausingle M1-N4 porphyrinic site · TCPP | 0D · Model SystemDFT monomer model for site-A screening | 2 · DFT Screening · Figure 1b |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Co-TCPP(Co)research_0509__mat__mat_co_tcpp_co | Nanosheet · Pristine Control · Mixed Metal | as-synthesised crystals/nanosheets | 3-4 · Morphological and Structural Characterization · Figure 2; Figure S6 |
| Cu-TCPP(Co)research_0509__mat__mat_cu_tcpp_co | Nanosheet · Pristine Control · Mixed Metal | as-synthesised crystals/nanosheets | 3-4 · Morphological and Structural Characterization · Figure 2; Figure S6 |
| Fe-TCPP(Co)research_0509__mat__mat_fe_tcpp_co | Nanosheet · Pristine Control · Mixed Metal | as-synthesised crystals/nanosheets | 3-4 · Morphological and Structural Characterization · Figure 2; Figure S6 |
| Ni-TCPP(Co)/CNT/Nafion on GDL flow-cell cathoderesearch_0509__mat__mat_ni_tcpp_co | Electrode · Composite Sample · Composite | catalyst ink coated on GDL, 100 ug catalyst loading, 1x1 cm active areaSGL-39BB gas-diffusion layer | S7 · Electrochemical tests in flow-cell |
| Mn-TCPP(Co)research_0509__mat__mat_mn_tcpp_co | Nanosheet · Pristine Control · Mixed Metal | as-synthesised crystals/nanosheets | 3-4 · Morphological and Structural Characterization · Figure 2; Figure S6 |
| M2-TCPP(Co) DFT supercell setresearch_0509__mat__mat_m2_tcpp_co_model | Model · Model System · Model | 2x2x1 periodic supercell | 3 · DFT Screening · Figure 1a |
| TCPP(M1) DFT monomer setresearch_0509__mat__mat_tcpp_m1_model | Model · Model System · Model | DFT geometry/model system | 2 · DFT Screening · Figure 1b |
| Ni-TCPP(Co) nanosheets/crystalsresearch_0509__mat__mat_ni_tcpp_co | Nanosheet · Target Sample · Mixed Metal | as-synthesised crystals/nanosheets | 3-4 · Morphological and Structural Characterization · Figure 2; Figure S6 |
| Ni-TCPP(Cu)research_0509__mat__mat_ni_tcpp_cu | Nanosheet · Pristine Control · Mixed Metal | as-synthesised crystals/nanosheets | 3-4 · Morphological and Structural Characterization · Figure 2; Figure S6 |
| Ni-TCPP(Mn)research_0509__mat__mat_ni_tcpp_mn | Nanosheet · Pristine Control · Mixed Metal | as-synthesised crystals/nanosheets | 3-4 · Morphological and Structural Characterization · Figure 2; Figure S6 |
| M2-TCPP(Co)/CNT/Nafion RRDE analogue seriesresearch_0509__mat__mat_m2_tcpp_co_model | Electrode · Composite Sample · Composite | 10 uL ink drop-cast on RRDErotating ring-disk electrode | S6 · Electrochemical Measurements |
| Ni-TCPP(Co)/CNT/Nafion RRDE catalyst layerresearch_0509__mat__mat_ni_tcpp_co | Electrode · Composite Sample · Composite | 10 uL ink drop-cast on RRDErotating ring-disk electrode | S6 · Electrochemical Measurements |