Osella S., Goddard III W.A. · Journal of the American Chemical Society · 2023 · 21319-21329
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.
Fine-tuning applied potential controls the methane/ethylene branch by changing the relative stability and barrier between *CHO and *CHOH; -1.2 V is predicted to maximise ethylene while suppressing methane.
Caveat: The potential-dependent selectivity comparison uses computed energies plus literature FE trends adapted from prior work.
main p.7, article p.21325 · 2.4 Optimizing the Ethylene Production Yield · Figure 5 · Linked to 4 structured results
The paper does not report a first-hand synthesis route for PcCu; it uses a literature MOF cell as the input structure for computational reoptimisation.
Caveat: The main text briefly states that PcCu can be obtained at the water-air interface and cites prior synthesis, but v2 computational-paper rules require no synthesis_routes for this purely theoretical paper.
main p.8, article p.21326 · 3. Experimental Section
CuPc is assigned as the main CO2RR catalytic centre because CO/CO2 bind favourably there and its d-band centre is closer to the Fermi level than the CuO4 sites.
Caveat: HER at CuO4 and strong CO-CuO4 binding at more negative bias are proposed as explanations for potential-dependent performance loss.
main p.8, article p.21326 · 2.4 Optimizing the Ethylene Production Yield · Figure 5d; Figure S9 · Linked to 4 structured results
The PcCu 2D MOF behaves like a single-atom catalyst for CO2 reduction because C2 production involves a single Cu site in the phthalocyanine core rather than a multi-Cu CO-CO dimerisation ensemble.
Caveat: This is a computational mechanism claim benchmarked against prior experimental FE trends, not a new direct experimental measurement.
main p.1, article p.21319 · Abstract · Linked to 2 structured results
The most probable calculated ethylene pathway is CO coupling into *CHO to form *(CHO)CO, followed by exergonic/barrierless or low-barrier steps; it avoids the usual CO-CO dimerisation mechanism.
Caveat: Pathway is computationally predicted using GCP-K and BEP-estimated barriers.
main p.7, article p.21325 · 2.3 Ethylene Formation Pathways · Figure 4 · Linked to 2 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| PcCu-based 2D metal-organic framework model catalyst | Not specifiedCu in the phthalocyanine core plus square-planar CuO4 nodes; the computational cell includes four K+ counterions coordinated to CuO4 oxygen atoms. · PcCu-(OH)8 macrocycle, described as [(2,3,9,10,16,17,23,24-octahydroxyphthalo-cyaninato)copper(II)]. | 2D · Model SystemPeriodic 2D phthalocyanine-based MOF model, labelled PcCu, with a monolayer basal plane and three Cu atoms per unit cell. | main p.3, article p.21321 · 2.1 Electronic Properties · Figure 1a |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| PcCu 2D MOF reaction model with adsorbates and water clusterresearch_0879__mat__pccu_2d_mof_model | Model · Model System · Model | Adsorbate, phthalocyanine core, and four-water-molecule cluster treated as movable during geometry optimisation; rest of MOF kept frozen to retain planarity.None; periodic computational monolayer. · Monolayer model with solvent cage. | main p.8, article p.21326 · 3. Experimental Section |
| Literature PcCu-Cu-O CO2RR electrode contextresearch_0879__mat__pccu_2d_mof_model | Electrode · Paper Level Unspecified · Pristine Framework | Prior experimental CO2RR sample cited from ref. 22; not prepared or measured first-hand in this paper.Cathode support mentioned for exfoliated monolayer/few-layer PcCu MOF in prior experimental work. · Not specified in this paper. | main p.2, article p.21320 · Introduction |
| Reoptimised pristine PcCu 2D MOF monolayer model cellresearch_0879__mat__pccu_2d_mof_model | Model · Model System · Model | QM-optimised model structure with 4 potassium counterions and S = 3/2 spin-polarised description.None; periodic computational monolayer with vacuum in z direction. · Monolayer model; 1.5 nm vacuum space in z direction. | main p.8, article p.21326 · 3. Experimental Section |