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Abstract The application of Co2‐xRhxP nanoparticles as electrocatalysts for the hydrogen evolution reaction (HER) and overall water splitting in basic media is reported. The experimental design seeks to dilute rhodium with earth‐abundant cobalt as a means to lower the cost of the material and achieve catalytic synergism, as reported for related bimetallic phosphides. The HER activity of Co2‐xRhxP is found to be composition‐dependent, with the rhodium‐rich compositions being more active as compared to their cobalt‐rich counterparts, with overpotentials (η) at 10 mA/cm2geometricof 58.1–63.9 mV vs. 82.1–188.1 mV, respectively. In contrast, Co‐rich Co2‐xRhxP nanoparticles are active for the oxygen evolution reaction (OER) process in basic media, with η= 290 mV for x=0.25. A full water electrolysis cell was created using the most active compositions for OER and HER as the anode and cathode, respectively, generating an overall η= 390 mV. Notably, the cell became more active over a 50 h stability test, increasing by 2 mV/cm2geometricat a constant applied voltage of 1.62 V vs NHE. This enhanced activity correlates with nanoscale phase segregation of Rh in the anode. Thus, the lower overpotential achieved for Co1.75Rh0.25P relative to Co2P, and the augmented activity over time in the former, may be a consequence of restructuring of the anode driven by Rh phase‐segregation. The augmentation in activity at the anode more than compensates for small losses at the cathode.
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Using Host‐Guest Chemistry to Examine the Effects of Porosity and Catalyst‐Support Interactions on CO 2 Reduction
Abstract Bis‐porphyrin nanocages (M2BiCage, M = FeCl, Co, Zn) and their host‐guest complexes with C60and C70were used to examine how molecular porosity and interactions with carbon nanomaterials affect the CO2reduction activity of metalloporphyrin electrocatalysts. The cages were found to adsorb on carbon black to provide electrocatalytic inks with excellent accessibilities of the metal sites (≈50%) even at high metal loadings (2500 nmol cm−2), enabling good activity for reducing CO2to CO. A complex of C70bound inside(FeCl)2BiCageachieves high current densities for CO formation at low overpotentials (|jCO| >7 mA cm−2,η= 320 mV; >13.5 mA cm−2,η= 520 mV) with ≥95% Faradaic efficiency (FECO), andCo2BiCageachieves high turnover frequencies (≈1300 h−1,η= 520 mV) with 90% FECO. In general, blocking the pore with C60or C70improves the catalytic performance of(FeCl)2BiCageand has only small effects onCo2BiCage, indicating that the good catalytic properties of the cages cannot be attributed to their internal pores. Neither enhanced electron transfer rates nor metal‐fullerene interactions appear to underlie the ability of C60/C70to improve the performance of(FeCl)2BiCage, in contrast to effects often proposed for other carbon nanosupports.
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- PAR ID:
- 10607232
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 64
- Issue:
- 21
- ISSN:
- 1433-7851
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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