CaveatSupport assessment: High
The authors note limitations: the ATR cell lacks temperature control, ATR only captures surface deposition, and fully reduced HHTP-tc could not be isolated.
p009 / journal page 1391 · Conclusions
Primary studyCore evidenceSynthesis Structure
Mechanistic Insight into the Formation and Deposition of Conductive, Layered Metal-Organic Framework Nanocrystals
Ambrogi E.K., Damacet P., Stolz R.M. et al. · ACS Nano · 2025 · 1383-1395
3materials
26samples
25synthesis routes
64measurements
143results
6claims and caveats
Evidence map
Open a family to keep every result attached to its sample, method and conditions.
Author interpretations and caveats
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
Phase AssignmentSupport assessment: Medium
Ni3(HHTP)2 products are assigned to a layered ABAB/intercalated-layer structure using PXRD comparison to an isostructural Co3(HHTP)2 simulation.
Caveat: The simulated pattern used a Co3(HHTP)2 CIF from CSD rather than a new Ni3(HHTP)2 single-crystal structure in this paper.
S7-S8 · PXRD assignment · Figure S7; Table S1 · Linked to 2 structured results
Structure Property LinkSupport assessment: High
Slower oxidant delivery favours rod-like nanocrystalline morphologies, whereas rapid/excess H2O2 accelerates growth and produces larger irregular aggregates.
Caveat: Morphology was assessed by SEM/TEM; no full kinetic model beyond initial rates was derived.
p006 / journal page 1388 · Correlation of growth rates · Figure 3 · Linked to 4 structured results
Synthesis MechanismSupport assessment: High
In situ ATR-FTIR shows an induction period followed by an approximately linear initial growth region at the diagnostic 1464 cm^-1 MOF band.
Caveat: ATR measures deposition onto the diamond surface, not directly all solution-phase nucleation events.
p005 / journal page 1387 · Mechanistic Insights · Figure 2 · Linked to 3 structured results
Synthesis MechanismSupport assessment: High
Oxidants are critical for Ni3(HHTP)2 crystallite formation; without oxygen or peroxide, the reaction stalls near coordination-complex formation and yields little/no MOF.
Caveat: N2 bulk still gave some product, likely from residual oxygen or imperfect exclusion.
p009 / journal page 1391 · Conclusions · Figure 6 · Linked to 3 structured results
Synthesis MechanismSupport assessment: High
At the HHTP/Ni concentrations used, dissolved O2 is much lower than HHTP and must be replenished; O2 diffusion controls rate under air-only conditions.
Caveat: O2 concentration was calculated from solubility rather than measured directly in the reaction cell.
S32-S34 · Oxidant Concentrations · Table S10 · Linked to 3 structured results
Material identities
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| reduced HHTP precursor | C18H12O6 (HHTP; oxidation state mixture, relatively reduced)none · HHTP precursor to Ni3(HHTP)2 | 0D · Model SystemMolecular precursor; seven oxidation states possible from tris-catecholate to tris-quinone. | S3-S4 · In-House Preparation and Characterization of HHTP · Figure S1 |
| Ni3(HHTP)2Browse family: Ni₃(HHTP)₂ / Ni–HHTP | Ni3(HHTP)2 used as a connectivity descriptor for the 2D coordinated layer; cobalt/nickel HHTP analogues also contain an intercalated layer and edge/defect/solvent sites not captured by the formulaNi2+ dominant redox state; nickel-catecholate/bis-dioxolene coordination nodes · 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) | 2D · PristineLayered conductive MOF; ABAB packing with conjugated and intercalated HHTP-metal layers, isostructural to Co3(HHTP)2 simulation used for PXRD assignment. | p003 / journal page 1385 · Experimental Design - Naming conventions |
| Ni-HHTP coordination complex in solutionBrowse family: Ni₃(HHTP)₂ / Ni–HHTP | solution-phase Ni2+-HHTP coordination complex; exact formula not isolatedNi2+ from nickel(II) acetate · HHTP | 0D · Model SystemTransient coordination complex/oligomer formed before oxidant-driven MOF crystallite growth. | p008 / journal page 1390 · Observations of the Initial Phase · Figure 5 |
Sample register
Sample form, processing state and composition status define the context for measurements.
Show 26 sample records
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| ATR air bubbled 1 mL/min Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR air bubbled 2 mL/min Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR air bubbled 4 mL/min Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR in situ air-bubbled Ni3(HHTP)2, room temperatureresearch_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | MOF deposited on ATR crystal from 20:3 H2O/DMF; remaining reaction mixture collected after 18 hdiamond ATR crystal | p004 / journal page 1386 · Figure 2 caption · Figure 2 |
| ATR air-diffusion port-in Ni3(HHTP)2, room temperatureresearch_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | Reaction cell open to air with smaller port-in aperturediamond ATR crystal | S34 · Oxidant concentrations · Figure S47 |
| ATR air-diffusion port-out Ni3(HHTP)2, room temperatureresearch_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | Reaction cell open to air; passive O2 diffusiondiamond ATR crystal | S34 · Oxidant concentrations · Figure S47 |
| ATR air plus 50 uL 6% H2O2 Ni3(HHTP)2, room temperatureresearch_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 50 uL 6% H2O2 added after Ni solution; cell also open to airdiamond ATR crystal | p004 / journal page 1386 · Figure 2 caption · Figure 2 |
| ATR 10 eq H2O2 Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR delayed 10 eq H2O2 Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR gradual 10 eq H2O2 over 2 h Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR gradual 10 eq H2O2 over 4 h Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR 1 eq H2O2 Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR 3 eq H2O2 Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR delayed 3 eq H2O2 Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR 5 eq H2O2 Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR 7.5 eq H2O2 Ni3(HHTP)2research_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | 20:3 H2O/DMF ATR-FTIR reaction at room temperaturediamond ATR crystal | S36-S42 · In-situ growth experiments · Tables S11-S16 |
| ATR nitrogen-control Ni3(HHTP)2 attempt, room temperatureresearch_0620__mat__mat_ni3_hhtp2 | Thin Film · Target Sample · Pristine Framework | N2 gas flowing over reaction solutiondiamond ATR crystal | p004 / journal page 1386 · Figure 2 caption · Figure 2 |
| homogeneous DMF/water air plus H2O2 Ni3(HHTP)2, 85 Cresearch_0620__mat__mat_ni3_hhtp2 | Powder · Target Sample · Pristine Framework | 20:3 H2O/DMF, bubbled air, 1 mL 6% H2O2, 85 C, 18 h; collected by centrifuging in SI figures | S11-S15 · Bulk synthesis samples · Table S3; Table S4; Figure S11 |
| heterogeneous water bubbled-air Ni3(HHTP)2, 85 Cresearch_0620__mat__mat_ni3_hhtp2 | Powder · Target Sample · Pristine Framework | Water-only heterogeneous synthesis, bubbled air, 85 C, 18 h; vacuum filtration | S7, S11, S14-S15 · Figure S6 and Table S3/S4 · Figure S6; Table S3; Table S4 |
| homogeneous DMF/water bubbled-air Ni3(HHTP)2, 22 Cresearch_0620__mat__mat_ni3_hhtp2 | Powder · Target Sample · Pristine Framework | 3:20 DMF:H2O, bubbled air, approximately 22 C, 18 h | S21-S22 · Impact of Temperature · Figure S28; Table S7 |
| homogeneous DMF/water bubbled-air Ni3(HHTP)2, 40 Cresearch_0620__mat__mat_ni3_hhtp2 | Powder · Target Sample · Pristine Framework | 3:20 DMF:H2O, bubbled air, 40 C, 18 h | S21-S22 · Impact of Temperature · Figure S28; Table S7 |
| homogeneous DMF/water bubbled-air Ni3(HHTP)2, 85 Cresearch_0620__mat__mat_ni3_hhtp2 | Powder · Target Sample · Pristine Framework | 20:3 H2O/DMF homogeneous synthesis, bubbled air, 85 C, 18 h; blue-black powder | S11, S14-S15 · Bulk synthesis samples · Table S3; Table S4 |
| homogeneous DMF/water N2 plus H2O2 Ni3(HHTP)2, 85 Cresearch_0620__mat__mat_ni3_hhtp2 | Powder · Target Sample · Pristine Framework | 20:3 H2O/DMF, bubbled N2, 1 mL 6% H2O2, 85 C, 18 h; collected by centrifuging in SI figures | S11-S15 · Bulk synthesis samples · Table S3; Table S4; Figure S12 |
| homogeneous DMF/water bubbled-N2 Ni3(HHTP)2, 85 Cresearch_0620__mat__mat_ni3_hhtp2 | Powder · Target Sample · Pristine Framework | 20:3 H2O/DMF homogeneous synthesis, bubbled N2, 85 C, 18 h | S11, S13-S15 · Bulk synthesis samples · Table S3; Table S4 |
| reduced HHTP powderresearch_0620__mat__mat_hhtp_precursor | Powder · Model System · Model | prepared from HMTP by BBr3 dealkylation; stored under vacuum | S3-S4 · Synthesis of reduced HHTP |
| Ni-HHTP solution complexresearch_0620__mat__mat_ni_hhtp_complex | Model · Model System · Model | HHTP solution mixed with Ni(OAc)2 solution before oxidant addition | p008 / journal page 1390 · Figure 5 caption · Figure 5 |