Reversed linkage-oriented intermolecular electron-transfer in isomeric covalent organic frameworks for electrochemical CO2 reduction
Bibliographic record
Abstract
Designing specific electroactive sites and modulating their local microenvironments of covalent organic frameworks (COFs) toward electrochemical CO 2 reduction (ECR) have received increasing attention. However, the underlying impact of the change in intramolecular electron-transfer capability, caused by the tuning in electronic state of active sites, on the redox-mediated catalytic process still remains inadequately understood. In this work, we constructed a metalloporphyrin-based COF as the isomer of the representative COF-367-Co, with an identical chemical composition but a reversed imine-linkage orientation via Schiff-base condensation reaction using [meso-tetrakis(4-formylphenyl)porphyrin]cobalt (CoTFPP) and Benzidine (BD) as the precursors, denoted as CoTFPP-BD-COF, to exclusively investigate the linkage orientation as an individual variable for enhanced electron transmission efficiency toward ECR. The CoTFPP-BD-COF exhibits impressively higher CO Faradaic efficiencies (FE CO ) of over 90 % than the benchmark COF-367-Co (below 50 %) within a wide potential range of 600 mV. The experimental and computational results collectively suggest that as compared to the isomeric COF-367-Co, the reversal of imine-linkage orientation in CoTFPP-BD-COF not only enhances the CO 2 adsorption capacity of active centers in cobalt porphyrin through tuning its electronic configuration, but also facilitates the intramolecular oriented electron-transfer by suppressing its electron donor effect, thereby synergistically facilitating ECR. This study exclusively demonstrates the linkage contribution in remote electronic tuning of COFs, and uncovers its associated mechanism toward electrosynthesis.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".