Electrochemistry Application — Solvothermal preparation of an electrocatalytic metalloporphyrin MOF thin film and its redox hopping charge-transfer mechanism

4 measurement groups · 21 results

Reported values remain attached to the sample, method, conditions, extraction quality and source location that produced them.

CCl4 reduction electrocatalysis by CV and UV-vis spectroelectrochemistry

UV-visible and optical absorption spectroscopy Voltammetry

CoPIZA/FTO thin film electrode · Electrode

CoPIZA/FTO in 0.1 M LiClO4/DMF; CV before/after CCl4 addition at 100 mV/s; film first reduced to (CoI TCPP)CoPIZA, then CCl4 injected and spectral changes monitored.

Geometry: CoPIZA/FTO electrode
Context: pristine CoPIZA/FTO target used as proof-of-concept electrocatalyst
Measurement source: 6 · Results and Discussion · Figure 7

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
CCl4 reduction catalytic current response	current increases in the presence of CCl4 at the (CoII/ITCPP)CoPIZA reduction potential	—	—	Qualitative Qualitative	6 · Results and Discussion · Figure 7A
spectroscopic assignment of active catalytic state	after CCl4 injection, spectral features consistent with (CoII TCPP)CoPIZA were recovered	—	—	Qualitative Qualitative	6 · Results and Discussion · Figure 7B

controlled potential electrolysis followed by SEM and solution UV-vis inspection

UV-visible and optical absorption spectroscopy Scanning electron microscopy

CoPIZA/FTO thin film electrode · Electrode

CoPIZA/FTO held at -1.04 V or -1.45 V vs ferrocyanide for 24 h; post-electrolysis SEM and solution spectra assessed film stability.

Geometry: CoPIZA/FTO electrode
Context: pristine CoPIZA/FTO target under prolonged electrolysis
Measurement source: 6 · Results and Discussion · Figures S8 and S9

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
long-term electrolysis stability at -1.04 V	no significant deterioration after 24 h at -1.04 V vs ferrocyanide	—	—	Text Qualitative	6 · Results and Discussion · Figure S8
long-term electrolysis degradation at -1.45 V	film appears pitted and dissolved CoTCPP features observed after 24 h at -1.45 V vs ferrocyanide	—	—	Text Qualitative	6 · Results and Discussion · Figure S9

cyclic voltammetry (CV)

Voltammetry

CoPIZA/FTO thin film electrode · Electrode

BASi Epsilon potentiostat; CoPIZA/FTO working electrode, platinum mesh counter electrode, Ag/AgCl saturated KCl reference; 0.1 M LiClO4/DMF electrolyte; Ag/AgCl calibrated against Fe(CN)6^3-/4-; representative scan at 100 mV/s.

Geometry: three-electrode cell with CoPIZA on FTO working electrode
Context: pristine CoPIZA/FTO target
Measurement source: 7 · Experimental Section - Electrochemistry · Figure 5; Table 1; Figure S4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
reverse-scan anodic peak potential	-0.975 V vs ferrocyanide	—	—	Text Exact Reported	3 · Results and Discussion · Figure 5
first cathodic peak potential	-1.1 V vs ferrocyanide	—	—	Text Rounded Reported	3 · Results and Discussion · Figure 5
second cathodic peak potential	-1.45 V vs ferrocyanide	—	—	Text Rounded Reported	3 · Results and Discussion · Figure 5
first redox event cathodic/anodic peak current	approximately 2.9 uA	0.0000029 A	—	Text Approximate	3 · Results and Discussion · Figure S4
first redox event peak separation	125 mV	0.125 V	—	Text Exact Reported	4 · Results and Discussion · Figure 5
linearity of peak current versus square root of scan rateMarked as a best value within this paper	R2 = 0.99	—	—	Text Exact Reported	4 · Results and Discussion · Figure 5 inset
linearity of peak current versus scan rate	R2 = 0.97	—	—	Text Exact Reported	4 · Results and Discussion · Figure 5 inset
CV cycling stability	>25 cycles without loss in peak current	—	—	Text Approximate	6 · Results and Discussion
E1/2 for (CoIII/IITCPP)CoPIZA from CVMarked as a best value within this paper	-1.04 V vs ferrocyanide	—	—	Table Exact Reported	5 · Results and Discussion · Table 1

spectroelectrochemistry

CoPIZA/FTO thin film electrode · Electrode

Three-electrode arrangement in N2-purged quartz cuvette; CoPIZA/FTO working electrode, platinum mesh counter, Ag/AgCl reference; 0.1 M LiClO4/DMF; potential applied with BASi Epsilon and spectra monitored by Cary UV-vis NIR.

Atmosphere: nitrogen purge for 1 h
Geometry: CoPIZA/FTO working electrode in quartz cuvette
Context: pristine CoPIZA/FTO target
Measurement source: 7 · Experimental Section - Spectroelectrochemistry · Figure 6; Figures S5-S7

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
built-in overpotential from film reduction	59 mV	0.059 V	—	Text Exact Reported	6 · Results and Discussion
apparent diffusion coefficient for redox-hopping charge transportMarked as a best value within this paper	7.55 (+/-0.05) x 10^-14 cm^2/s	7.55e-18 m^2 s^-1	+/-0.05 x 10^-14 cm^2/s	Text Exact Reported	5 · Results and Discussion · Figure S7; Equation 6
potential needed for order-of-magnitude reduced/oxidised changeMarked as a best value within this paper	118 mV per decade	0.118 V per decade	—	Text Exact Reported	5 · Results and Discussion · Equations 4-5
precise E1/2 for (CoII/ITCPP)CoPIZA transitionMarked as a best value within this paper	-1386 +/- 6 mV vs ferrocyanide	-1.386 V vs ferrocyanide	+/- 6 mV	Text Exact Reported	5 · Results and Discussion · Figure 6
isosbestic points for Co(II/I TCPP)CoPIZA transition	390 and 449 nm	—	—	Text Rounded Reported	4 · Results and Discussion · Figure S6
isosbestic points for Co(III/II TCPP)CoPIZA transition	430, 458, and 544 nm	—	—	Text Rounded Reported	4 · Results and Discussion · Figure S5
modified Nernst nonideality factorMarked as a best value within this paper	2	—	—	Text Exact Reported	5 · Results and Discussion · Figure 6
E1/2 for (CoII/ITCPP)CoPIZA from spectroelectrochemistryMarked as a best value within this paper	-1.39 V vs ferrocyanide	—	—	Table Rounded Reported	5 · Results and Discussion · Table 1