CO2-Promoted Electrocatalytic Reduction of Chlorinated Hydrocarbons.

Electrochemical reactions and their catalysis are important for energy and environmental applications, such as carbon neutralization and water purification. However, the synergy in electrocatalysis between CO2 utilization and wastewater treatment has not been explored. In this study, we find that the electrochemical reduction of chlorinated organic compounds such as 1,2-dichloroethane, trichloroethylene, and tetrachloroethylene into ethylene in aqueous media, which is a category of challenging reactions due to the competition of H2 evolution, can be substantially enhanced by simultaneously carrying out the reduction of CO2 on an easily prepared and cost-effective Cu metal catalyst. In the case of 1,2-dichloroethane dechlorination, a 6-fold improvement in Faradaic efficiency and a 19-fold increase in partial current density are demonstrated. Through electrochemical kinetic studies, in situ Raman spectroscopy, and computational simulations, we further find that CO2 reduction reduces hydrogen coverage on the Cu catalyst, which not only exposes more active sites for the dechlorination reaction but also enhances the effective reductive potential on the catalyst surface and reduces the kinetic barrier of the rate-determining step.

Tailoring Interfaces for Enhanced Methanol Production from Photoelectrochemical CO2 Reduction.

Efficient and stable photoelectrochemical reduction of CO2 into highly reduced liquid fuels remains a formidable challenge, which requires an innovative semiconductor/catalyst interface to tackle. In this study, we introduce a strategy involving the fabrication of a silicon micropillar array structure coated with a superhydrophobic fluorinated carbon layer for the photoelectrochemical conversion of CO2 into methanol. The pillars increase the electrode surface area, improve catalyst loading and adhesion without compromising light absorption, and help confine gaseous intermediates near the catalyst surface. The superhydrophobic coating passivates parasitic side reactions and further enhances local accumulation of reaction intermediates. Upon one-electron reduction of the molecular catalyst, the semiconductor-catalyst interface changes from adaptive to buried junctions, providing a sufficient thermodynamic driving force for CO2 reduction. These structures together create a unique microenvironment for effective reduction of CO2 to methanol, leading to a remarkable Faradaic efficiency reaching 20% together with a partial current density of 3.4 mA cm-2, surpassing the previous record based on planar silicon photoelectrodes by a notable factor of 17. This work demonstrates a new pathway for enhancing photoelectrocatalytic CO2 reduction through meticulous interface and microenvironment tailoring and sets a benchmark for both Faradaic efficiency and current density in solar liquid fuel production.

Active Sites of Cobalt Phthalocyanine in Electrocatalytic CO2 Reduction to Methanol.

Many metal coordination compounds catalyze CO2 electroreduction to CO, but cobalt phthalocyanine hybridized with conductive carbon such as carbon nanotubes is currently the only one that can generate methanol. The underlying structure-reactivity correlation and reaction mechanism desperately demand elucidation. Here we report the first in situ X-ray absorption spectroscopy characterization, combined with ex situ spectroscopic and electrocatalytic measurements, to study CoPc-catalyzed CO2 reduction to methanol. Molecular dispersion of CoPc on CNT surfaces, as evidenced by the observed electronic interaction between the two, is crucial to fast electron transfer to the active sites and multi-electron CO2 reduction. CO, the key intermediate in the CO2 -to-methanol pathway, is found to be labile on the active site, which necessitates a high local concentration in the microenvironment to compete with CO2 for active sites and promote methanol production. A comparison of the electrocatalytic performance of structurally related porphyrins indicates that the bridging aza-N atoms of the Pc macrocycle are critical components of the CoPc active site that produces methanol. In situ X-ray absorption spectroscopy identifies the active site as Co(I) and supports an increasingly non-centrosymmetric Co coordination environment at negative applied potential, likely due to the formation of a Co-CO adduct during the catalysis.

Pulsed Electrolysis of Boron-Doped Carbon Dramatically Improves Impurity Tolerance and Longevity of H2O2 Production.

Electrocatalytic water treatment has emerged in the limelight of scientific interest, yet its long-term viability remains largely in the dark. Herein, we present for the first time a comprehensive framework on how to optimize pulsed electrolysis to bolster catalyst impurity tolerance and overall longevity. By examining real wastewater constituents and assessing different catalyst designs, we deconvolute the complexities associated with key pulsing parameters to formulate optimal sequences that maximize operational lifetime. We showcase our approach for cathodic H2O2 electrosynthesis, selected for its widespread importance to wastewater treatment. Our results unveil superior performance for a boron-doped carbon catalyst over state-of-the-art oxidized carbon, with high selectivity (>75%) and near complete recoveries in overpotentials even in the presence of highly detrimental Ni2+ and Zn2+ impurities. We then adapt these fine-tuned settings, obtained under a three-electrode arrangement, for practical two-electrode operation using a novel strategy that conserves the desired electrochemical potentials at the catalytic interface. Even under various impurity concentrations, our pulses substantially improve long-term H2O2 production to 287 h and 35 times that attainable via conventional electrolysis. Our findings underscore the versatility of pulsed electrolysis necessary for developing more practical water treatment technologies.

Synergizing Electron and Heat Flows in Photocatalyst for Direct Conversion of Captured CO2.

We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO2 reduction by synergizing electron and heat flows in the photocatalyst. The photocatalyst comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) that are decorated with nearly monodispersed cadmium sulfide quantum dots (CdS QDs). The CdS QDs absorb visible light and generate electron-hole pairs. The CNTs rapidly transfer the photogenerated electrons from CdS to CoPc. The CoPc molecules then selectively reduce CO2 to CO. The interfacial dynamics and catalytic behavior are clearly revealed by time-resolved and in situ vibrational spectroscopies. In addition to serving as electron highways, the black body property of the CNT component can create local photothermal heating to activate amine-captured CO2 , namely carbamates, for direct photochemical conversion without additional energy input.