Sun H., Chen L., Xiong L. et al. · Nature Communications · 2021 · 6823
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.
The KB support effect extends to another semiconductive Cu MOF, Cu3(HHTP)2, where KB-supported samples also show stabilised ethylene production and particle size.
Caveat: HHTP extension is supported mainly by SI figures and qualitative text; no quantitative HHTP particle-size table is provided.
8 · Universality of the observations · Supplementary Figs. 30-33 · Linked to 5 structured results
Adding Ketjen Black to semiconductive Cu3(HITP)2 greatly promotes and stabilises ethylene production over a wide potential window compared with stand-alone Cu3(HITP)2.
Caveat: Application performance is for electrochemically reconstructed catalyst states, not a permanently pristine MOF active site.
8 · Discussion · Linked to 4 structured results
Rich grain boundaries, multifacets and under-coordinated sites on Cu-RNP-like crystallites enhance CO adsorption and favour C-C coupling toward C2H4 over CH4.
Caveat: DFT model represents post-electrolytic surface motifs rather than atomically exact experimental structures.
7 · Mechanistic comprehension · Fig. 5 · Linked to 5 structured results
The Cu-RNP-like post-electrolytic surface from KB@Cu3(HITP)2 falls in the CO2RR-dominant zone, whereas Cu(111) surface sites fall in the HER-dominant zone.
Caveat: The selectivity map is from calculated *H and *CO binding energies; the key numerical values are mainly graphical and were not digitised.
7 · Mechanistic comprehension · Fig. 5d-e · Linked to 3 structured results
MOF-derived Cu crystallites outperform KB-supported naked Cu nanoparticles because the MOF precursor yields stabilised, lattice-diverse Cu motifs and possibly residual-ligand tethering.
Caveat: Residual-ligand tethering is proposed rather than directly isolated.
6 · Control studies with naked Cu nanoparticles · Supplementary Figs. 13-15 · Linked to 3 structured results
The conducting KB support provides higher current density and charge delocalisation, accelerating Cu-node reduction while suppressing aggregation of reduced Cu crystallites.
Caveat: Mechanism is inferred from operando XAS, ex situ XRD/TEM and analogy to charge delocalisation in battery SEI systems.
5 · Ex situ time-lapse XRD and TEM · Figs. 3-4 · Linked to 4 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Cu(111) surface model | Cu(111)Cu atoms | 2D · Model SystemDFT model for post-electrolytic Cu3(HITP)2 represented by a 4 x 4 x 4 Cu(111) supercell. | 6 · Mechanistic comprehension · Supplementary Fig. 20 |
| Cu3(HHTP)2Browse family: Cu₃(HHTP)₂ / Cu–HHTP | Cu3(HHTP)2; HHTP = 2,3,6,7,10,11-hexahydroxytriphenyleneCu nodes · 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) | 2D · PristineSimilar semiconductive Cu MOF used to test whether the Ketjen Black effect extends beyond Cu3(HITP)2. | 8 · Universality of the observations · Supplementary Figs. 30-33 |
| Cu3(HITP)2Browse family: Cu₃(HITP)₂ / Cu–HITP | Cu3(HITP)2; HITP = 2,3,6,7,10,11-hexaiminotriphenyleneCu nodes with mixed Cu2+ and Cu+ states in the pristine MOF · 2,3,6,7,10,11-hexaiminotriphenylene (HITP), prepared from HATP.6HCl | 2D · PristineSemiconductive crystalline conductive MOF with prominent XRD peaks between 3 and 30 degrees, rod-like nanocrystals, in-plane electron delocalisation and through-space charge transport. | 2 · Results - Structural characterization of Cu3(HITP)2 · Fig. 1 |
| Cu rectangular nanopyramid model | Cu-RNP on Cu(101)Cu atoms | 0D · Model SystemDFT model for post-electrolytic KB@Cu3(HITP)2: [101] Cu rectangular nanopyramids on a 5 x 5 x 1 Cu(101) surface with adjacent (100) and (111) facets. | 6 · Mechanistic comprehension · Fig. 5c; Supplementary Fig. 19 |
| KB@Cu3(HHTP)2Browse family: Cu₃(HHTP)₂ / Cu–HHTP | Cu3(HHTP)2 plus Ketjen BlackCu nodes from Cu3(HHTP)2, reconstructed during CO2RR · HHTP-derived residual ligands after reconstruction | 2D · CompositeConductive carbon-supported Cu3(HHTP)2 composite catalyst. | 8 · Universality of the observations · Supplementary Fig. 32 |
| KB@Cu3(HITP)2Browse family: Cu₃(HITP)₂ / Cu–HITP | Cu3(HITP)2 plus Ketjen BlackCu nodes from Cu3(HITP)2, reduced to Cu0 crystallites under CO2RR · HITP-derived residual ligands after reconstruction | 2D · CompositeComposite catalyst/electrode of semiconductive Cu3(HITP)2 and conductive Ketjen Black; during CO2RR it rapidly forms and stabilises small Cu0 crystallites. | 2 · CO2RR of Cu3(HITP)2 with or without KB · Fig. 1a |
| KB@CuNPs | Commercial Cu nanoparticles plus Ketjen BlackCu metal nanoparticles | 0D · CompositeNaked commercial Cu nanoparticles (10-30 nm) dispersed with Ketjen Black as a non-MOF control. | 6 · Control studies with naked Cu nanoparticles · Supplementary Figs. 13-15 |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Cu(111) model for post-electrolytic Cu3(HITP)2research_0479__mat__cu111_model | Model · Model System · Model | DFT relaxed Cu(111) slab model.4 x 4 x 4 Cu(111) supercell | 9 · Methods - Computational methods |
| Stand-alone Cu3(HHTP)2 CO2RR electroderesearch_0479__mat__cu3_hhtp2 | Electrode · Pristine Control · Pristine Framework | Cu3(HHTP)2 tested without conducting KB support.CO2RR electrode | 8 · Universality of the observations · Supplementary Fig. 32 |
| As-synthesised Cu3(HHTP)2 powderresearch_0479__mat__cu3_hhtp2 | Powder · Pristine Control · Pristine Framework | As-synthesised blue powder, centrifuged, washed and dried under vacuum. | 9 · Methods - Synthesis of Cu3(HHTP)2 |
| Stand-alone Cu3(HITP)2 CO2RR electroderesearch_0479__mat__cu3_hitp2 | Electrode · Pristine Control · Pristine Framework | Cu3(HITP)2 catalyst electrode tested without Ketjen Black conducting support.Glassy carbon for H-cell testing; carbon paper for ex situ XRD; gas diffusion electrode for flow cell testing | 2 · CO2RR of Cu3(HITP)2 with or without KB · Fig. 2 |
| As-synthesised Cu3(HITP)2 powderresearch_0479__mat__cu3_hitp2 | Powder · Pristine Control · Pristine Framework | As-synthesised black powder, washed and dried under vacuum. | 9 · Methods - Synthesis of Cu3(HITP)2 |
| Cu-RNP model for post-electrolytic KB@Cu3(HITP)2research_0479__mat__cu_rnp_model | Model · Model System · Model | DFT relaxed Cu rectangular nanopyramid model with (100) and (111) sidewall facets.5 x 5 x 1 Cu(101) surface | 9 · Methods - Computational methods |
| KB@Cu3(HHTP)2 CO2RR electroderesearch_0479__mat__kb_cu3_hhtp2 | Electrode · Target Sample · Composite | Cu3(HHTP)2 tested with Ketjen Black conducting support.CO2RR electrode | 8 · Universality of the observations · Supplementary Fig. 32 |
| KB@Cu3(HITP)2 CO2RR electroderesearch_0479__mat__kb_cu3_hitp2 | Electrode · Target Sample · Composite | Cu3(HITP)2 mixed with Ketjen Black conducting agent and tested for CO2RR.Glassy carbon for H-cell testing; carbon paper for ex situ XRD; gas diffusion electrode for flow cell testing · Flow-cell catalyst loading 0.8 mg cm-2 | 9 · Methods - Electrochemical measurements |
| KB@CuNPs control electroderesearch_0479__mat__kb_cunps | Electrode · Pristine Control · Composite | Commercial Cu nanoparticles dispersed with Ketjen Black and tested under CO2RR.H-cell electrode | 6 · Control studies with naked Cu nanoparticles · Supplementary Figs. 13-15 |
| Post-electrolytic Cu3(HHTP)2 after CO2RRresearch_0479__mat__cu3_hhtp2 | Electrode · Pristine Control · Derived Carbon | Post-CO2RR stand-alone Cu3(HHTP)2 after 0.25 h at varying potentials.CO2RR electrode after testing | 18 · Figures and Tables · Supplementary Fig. 33 |
| Post-electrolytic Cu3(HITP)2 after CO2RRresearch_0479__mat__cu3_hitp2 | Electrode · Pristine Control · Derived Carbon | Electrochemically reconstructed stand-alone MOF with larger aggregated Cu particles.CO2RR electrode after testing | 5 · Ex situ time-lapse XRD and TEM · Fig. 4g-j |
| Post-electrolytic KB@Cu3(HHTP)2 after CO2RRresearch_0479__mat__kb_cu3_hhtp2 | Electrode · Target Sample · Derived Carbon | Post-CO2RR sample after 0.25 h at varying potentials.CO2RR electrode after testing | 18 · Figures and Tables · Supplementary Fig. 33 |
| Post-electrolytic KB@Cu3(HITP)2 after CO2RRresearch_0479__mat__kb_cu3_hitp2 | Electrode · Target Sample · Derived Carbon | Electrochemically reconstructed after CO2RR; Cu nodes reduced to small Cu0 crystallites dispersed with carbon and residual ligand-derived matrix.Carbon-containing electrode matrix after CO2RR | 6 · Mechanistic comprehension · Fig. 5a; Supplementary Figs. 16-17 |