Lu Y., Zhong H., Li J. et al. · Angewandte Chemie - International Edition · 2022 · e202208163
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.
Cu3HHAE2 is presented as the first sp-carbon embedded conductive 2D MOF direct photocathode for PEC hydrogen generation, reaching about 260 uA cm-2 at 0 V vs RHE.
Caveat: The record/application claim is within the paper's chosen comparison set of cocatalyst-free organic photocathodes; no independent benchmarking was performed here.
5 · Conclusion · Linked to 3 structured results
The Cu3HHAE2 framework electrode outperforms HHAE and bare Cu foam controls in photocurrent, IPCE, charge-transfer resistance and carrier-separation efficiency.
Caveat: The application sample is a drop-cast catalyst/Cu-foam electrode; substrate adhesion affects long-term stability.
4 · PEC HER measurement · Figure 4 · Linked to 8 structured results
Post-durability XRD, SEM, elemental mapping, XPS, FT-IR and Raman indicate retained chemical states and crystalline structure, while photocurrent slightly decreases because catalyst may peel from Cu foam.
Caveat: The durability conclusion is mainly qualitative in the text and figure; the amount of photocurrent loss is not numerically reported.
4 · PEC HER measurement · Figures S2, S11-S14 · Linked to 2 structured results
cRED, PXRD/Rietveld refinement, HRTEM and SAED support assignment of Cu3HHAE2 as a crystalline eclipsed kagome 2D c-MOF with hexagonal and triangular dual pores.
Caveat: No CIF was supplied in the assignment, but the main text and SI report the electron-diffraction/PXRD structure workflow and metrics.
3 · Structure characterisation · Figure 2 · Linked to 6 structured results
Operando Raman and DFT calculations support assignment of the acetylene/sp-carbon sites, rather than Cu or O SBU sites, as active centres for PEC HER.
Caveat: Active-site assignment is inferred from spectroscopy and computational free energies; no isotope-labelling or direct intermediate structure is reported.
5 · Theoretical calculation and conclusion · Figure 5 · Linked to 5 structured results
Cu3HHAE2 shows apparent semiconducting behaviour with thermally activated hopping transport.
Caveat: Bulk pellet conductivity is low and measured on pressed powder; no single-crystal or oriented-film mobility is reported.
3 · Electrical transport · Figure 3a,b · Linked to 3 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| Cu3HHAE2 sp-carbon embedded conductive 2D conjugated MOF | Cu3HHAE2; elemental formula reported as Cu3(C24H6O6)2square-planar CuO4 units from Cu2+ cations · hexahydroxyarylene-ethynylene macrocycle ligand (HHAE) with acetylene/sp-carbon units | 2D · PristineFully eclipsed layered kagome (kgm) 2D c-MOF with honeycomb-like arrangement, dual hexagonal/triangular pores, and pi-pi stacking. | 2 · Results and discussion · Figure 1a; Figure 2 |
| Cu3HHAE2 pore-wall DFT model | section of one full HHAE ligand and three half SBUsCuO4 SBU fragments · HHAE ligand fragment | 2D · Model SystemComputational model cut from the experimentally determined single-crystal structure. | 5 · Theoretical calculation · Figure 5b |
| Cu foam substrate/current collector | Cu | unknown · UnknownCommercial Cu foam used as photocathode substrate/control. | 4 · PEC HER measurement · Figure 4a |
| HHAE hexahydroxyarylene-ethynylene macrocycle ligand | HHAEhexahydroxyarylene-ethynylene macrocycle | 0D · UnknownMolecular monomer/ligand used as precursor and photocathode control. | 2 · Results and discussion · Figure 1a |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| as-synthesised Cu3HHAE2 powder/hexagonal rodsresearch_0783__mat__cu3hhae2_mof | Powder · Target Sample · Pristine Framework | Solvothermal product filtered, washed with water and acetone, and dried under vacuum; SEM showed hexagonal rods. | 6 · Section S2 Synthetic procedures |
| Cu3HHAE2 photocathode on Cu foamresearch_0783__mat__cu3hhae2_mof | Electrode · Target Sample · Composite | 1 mg Cu3HHAE2 dispersed in 200 uL isopropanol, sonicated at least 30 min and drop-cast onto acid/solvent-washed Cu foam; catalyst loading about 1 mg cm-2.Cu foam | 3 · Electrode preparation |
| Cu3HHAE2 pore-wall computational modelresearch_0783__mat__cu3hhae2_pore_wall_model | Model · Model System · Model | One full ligand and three half SBUs cut from the single-crystal structure for DFT HER calculations. | 4 · Modeling and First-principles calculations |
| Cu3HHAE2 pressed powder pellet with four silver-wire probesresearch_0783__mat__cu3hhae2_mof | Pellet · Target Sample · Pristine Framework | 8 mg sample pressed at room temperature; four silver-wire probes attached with conductive silver paste and dried in air for 1 h.polymer film during pressing; silver wire contacts · measured but value not reported | 3 · Electrical conductivity |
| Cu3HHAE2 drop-cast film on quartz glassresearch_0783__mat__cu3hhae2_mof | Thin Film · Target Sample · Composite | Catalyst drop-cast on quartz glass for transmission UV/vis absorption.quartz glass | 2 · Methods |
| Cu3HHAE2 single crystals for cREDresearch_0783__mat__cu3hhae2_mof | Single Crystal · Target Sample · Pristine Framework | Powder crushed, dispersed in absolute ethanol, ultrasonicated and transferred to grid; cRED collected at 96 K.holey carbon film covered copper grid for cRED | 5 · cRED data collection |
| bare Cu foam electroderesearch_0783__mat__cu_foam | Electrode · Pristine Control · Unknown | Bare Cu foam tested under identical PEC conditions.Cu foam | 4 · PEC HER measurement · Figure 4a |
| HHAE monomer cathode on Cu foamresearch_0783__mat__hhae_ligand | Electrode · Pristine Control · Composite | Prepared by the same catalyst ink/drop-cast electrode method as Cu3HHAE2, using HHAE as control catalyst.Cu foam | 4 · PEC HER measurement · Figure 4 |
| HHAE monomerresearch_0783__mat__hhae_ligand | Powder · Pristine Control · Unknown | Synthesised following a previously reported literature procedure. | 6 · Monomer(HHAE) synthesis |
| HHAE ligand film on quartz glassresearch_0783__mat__hhae_ligand | Thin Film · Pristine Control · Composite | Drop-cast on quartz glass for UV-vis-NIR comparison.quartz glass | 16 · Figure S10 caption · Figure S10 |