Nishihara H., Hirota T., Matsuura K. et al. · Nature Communications · 2017 · 109
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.
Selective CO2-to-CO electrocatalysis in Ni2-CPDPy973(1) is attributed to Ni-N4 sites embedded in a conductive carbonaceous framework.
Caveat: Partial current densities are estimated from the plotted figure; FE values are text-reported.
7 · Electrochemical catalysis · Fig. 6 · Linked to 5 structured results
The target conductive materials are derived carbonaceous frameworks from an organic molecular crystal, not first-hand conductive MOFs.
Caveat: The introduction discusses MOF-derived carbons in the broader literature, but the reported precursor is a cyclic porphyrin dimer organic crystal.
1 · Abstract · Linked to 3 structured results
The present OCFs are poorly porous; BET surface area decreases from 48 to 14 m2 g-1 when carbonisation temperature increases from 873 to 973 K.
Caveat: CO2 pore volume for Ni2-CPDPy973(1) was not measured.
24 · Supplementary Table 2 · Supplementary Table 2 · Linked to 4 structured results
The Ni-N4 coordination environment is largely retained in the carbonised OCFs.
Caveat: Ni2-CPDPy973(1) also shows evidence for a small metallic Ni contribution.
6 · Chemical environment of Ni in the carbon matrix · Fig. 5 · Linked to 4 structured results
Ni in the porphyrin centre stabilises the precursor against thermochemical decomposition, improving carbon yield and retention of ordered structure relative to H4-CPDPy.
Caveat: Comparison is between Ni-containing and free-base porphyrin dimers; other metals were not experimentally extracted here.
2 · Carbonization of Ni2-CPDPy · Fig. 1 · Linked to 4 structured results
Ni2-CPDPy crystals thermally convert first into a crystalline covalent-organic framework intermediate and then into ordered carbonaceous frameworks.
Caveat: Starting precursor synthesis details are external to this paper.
7 · Discussion · Linked to 3 structured results
Carbonisation generates electrically conductive OCFs; Ni2-CPDPy873(1) and Ni2-CPDPy973(1) show semiconducting resistivity behaviour.
Caveat: Transport samples included PTFE binder for carbonised samples; Ni2-CPDPy973(1) used four-probe geometry while 873 K sample used two-electrode method.
6 · Chemical structure transition upon carbonization · Supplementary Fig. 13 · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| H4-CPDPy free-base porphyrin dimer control | Not specifiedNone; free-base porphyrin · Free-base cyclic porphyrin dimer with diacetylene moieties | unknown · PristineLow-crystallinity free-base control; broad PXRD peaks and poor ordered-structure retention after pyrolysis. | 9 · Supplementary Figure 7 caption · Supplementary Fig. 7 |
| Ni2-CPDPy guest-free cyclic porphyrin dimer crystal | C92H48N12Ni2Two square-planar Ni-N4 porphyrin centres per cyclic dimer · Cyclic porphyrin dimer with butadiyne (diacetylene), phenyl, and meso-pyridyl groups | 3D · PristineGuest-free molecular crystal; monoclinic P21/c from PXRD/Rietveld refinement; columnar packing with diacetylene moieties aligned for solid-state polymerisation. | 2-4 · Results; Crystallographic structural changes upon carbonization · Fig. 2; Supplementary Fig. 2 |
| Ni2-CPDPy593(0) crystalline covalent-organic framework intermediate | C92H48N12Ni2Retained square-planar Ni-N4 porphyrin centres · Poly(diacetylene) backbone cross-linking CPDPy units | 2D · PristineCrystalline polymer/COF intermediate; stacked two-dimensional sheets after thermal polymerisation at 593 K. | 4 · Crystallographic structural changes upon carbonization · Fig. 2h-j; Supplementary Fig. 4-5 |
| Ni2-CPDPy873(1) ordered carbonaceous framework | C/N/Ni/H/O carbonaceous framework derived from Ni2-CPDPyMostly retained Ni-N4 units embedded in carbonaceous matrix · Carbonaceous framework from porphyrin, phenyl, pyridyl, and polydiacetylene moieties | 3D · DerivedOrdered carbonaceous framework retaining periodicity from the precursor polymer; defective graphene-like sheets with embedded Ni-N4 sites. | 4-6 · Crystallographic structural changes; Chemical environment of Ni · Fig. 2m; Fig. 5 |
| Ni2-CPDPy973(1) ordered carbonaceous framework | C/N/Ni/H/O carbonaceous framework derived from Ni2-CPDPyPredominantly retained Ni-N4 units with minor metallic Ni contribution · Carbonaceous framework from Ni2-CPDPy-derived aromatic and polydiacetylene fragments | 3D · DerivedHigher-temperature OCF retaining structural regularity with small shrinkage; conductive and catalytically active for CO2-to-CO. | 4,7 · Crystallographic structural changes; Electrochemical catalysis · Fig. 2g; Fig. 6 |
| Ni-TPP973(1) conventional Ni/N/C reference | Ni/N/CDisordered Ni species and Ni metal aggregates · Carbonised nickel tetraphenylporphyrin-derived carbonaceous matrix | unknown · CompositeDisordered Ni/N/C composite from carbonised Ni-TPP; Ni-N bonds cleaved and Ni metal formed. | 21 · Supplementary Figure 18 caption · Supplementary Fig. 18 |
| Zeolite-templated carbon reference | CNone · sp2 carbon framework | 3D · DerivedReference ordered microporous carbon with 13.8 Angstrom periodicity. | 7 · Electrochemical catalysis · Fig. 6d |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| H4-CPDPyresearch_0458__mat__mat_h4_cpdpy | Powder · Pristine Control · Pristine Framework | Free-base organic control before heat treatment. | 2 · Carbonization of Ni2-CPDPy · Fig. 1b,d |
| H4-CPDPy873(1)research_0458__mat__mat_h4_cpdpy | Powder · Pristine Control · Derived Carbon | Free-base control heated to 873 K for 1 h. | 9 · Supplementary Figure 7 caption · Supplementary Fig. 7 |
| Ni2-CPDPyresearch_0458__mat__mat_ni2_cpdpy | Powder · Target Sample · Pristine Framework | Guest-free organic crystal precursor; uncarbonised. | 4 · Crystallographic structural changes upon carbonization · Fig. 2a |
| Ni2-CPDPy593(0)research_0458__mat__mat_ni2_cpdpy593 | Powder · Target Sample · Pristine Framework | Heated to 593 K and stopped immediately; polymerised COF intermediate. | 3 · Fig. 2 caption · Fig. 2b |
| Ni2-CPDPy873(1)research_0458__mat__mat_ni2_cpdpy873_ocf | Powder · Target Sample · Derived Carbon | Carbonised at 873 K for 1 h under N2 flow. | 3 · Fig. 2 caption · Fig. 2c,m |
| Ni2-CPDPy973(1)research_0458__mat__mat_ni2_cpdpy973_ocf | Powder · Target Sample · Derived Carbon | Carbonised at 973 K for 1 h under N2 flow. | 4,7 · Crystallographic structural changes; Electrochemical catalysis · Fig. 2g; Fig. 6 |
| Ni2-CPDPy973(1)/Nafion catalyst layerresearch_0458__mat__mat_ni2_cpdpy973_ocf | Electrode · Composite Sample · Composite | Catalyst ink drop-cast from sample and Nafion solution.glassy carbon plate | 27 · Evaluation of selective CO2 reduction into CO · Supplementary Methods |
| Ni2-CPDPy/Nafion catalyst layerresearch_0458__mat__mat_ni2_cpdpy | Electrode · Composite Sample · Composite | Pristine organic crystal mixed with Nafion and drop-cast.glassy carbon plate | 27 · Evaluation of selective CO2 reduction into CO · Supplementary Methods |
| Ni-TPP973(1)research_0458__mat__mat_nitpp973 | Powder · Pristine Control · Composite | Nickel tetraphenylporphyrin carbonised at 973 K for 1 h. | 7 · Electrochemical catalysis · Fig. 6 |
| Ni-TPP973(1)/Nafion catalyst layerresearch_0458__mat__mat_nitpp973 | Electrode · Composite Sample · Composite | Conventional Ni/N/C control mixed with Nafion and drop-cast.glassy carbon plate | 27 · Evaluation of selective CO2 reduction into CO · Supplementary Methods |
| ZTCresearch_0458__mat__mat_ztc | Powder · Pristine Control · Derived Carbon | Reference zeolite-templated ordered microporous carbon. | 7 · Electrochemical catalysis · Fig. 6d |
| ZTC/Nafion catalyst layerresearch_0458__mat__mat_ztc | Electrode · Composite Sample · Composite | Reference carbon catalyst layer with Nafion.glassy carbon plate | 27 · Evaluation of selective CO2 reduction into CO · Supplementary Methods |