Nitrogen doped tin oxide nanostructured catalysts for selective electrochemical reduction of carbon dioxide to formate
TL;DR: In this paper, a tin oxide material with nitrogen doping by using ammonia treatment at elevated temperature was reported, and the N doped material demonstrated enhanced electrocatalytic CO2 reduction activity, showing high Faradaic efficiency (90%) for formate at -0.65
About: This article is published in Journal of Energy Chemistry.The article was published on 2017-09-01. It has received 41 citations till now. The article focuses on the topics: Tin oxide & Formate.
Citations
More filters
TL;DR: The mechanistic workings of an electrochemically deposited CuS x catalyst that can reduce CO2 to formate with a Faradaic efficiency of 75% and geometric current density of -9.0 mA/cm2 at -0.9 V is described.
Abstract: The efficient electroreduction of CO2 has received significant attention as it is one of the crucial means to develop a closed-loop anthropogenic carbon cycle. Here, we describe the mechanistic workings of an electrochemically deposited CuSx catalyst that can reduce CO2 to formate with a Faradaic efficiency (FEHCOO–) of 75% and geometric current density (jHCOO–) of −9.0 mA/cm2 at −0.9 V versus the reversible hydrogen electrode. At this potential, the formation of other CO2 reduction products such as hydrocarbons and CO was notably suppressed (total FE < 4%). The formate intermediate (HCOO*) was identified by operando Raman spectroscopy with isotopic labeling. A combination of electrochemical and materials characterization techniques revealed that the high selectivity toward formate production can be attributed to the effect of S dopants on the Cu catalyst, rather than surface morphology. Density functional theory calculations showed that the presence of sulfur weakens the HCOO* and *COOH adsorption energi...
127 citations
TL;DR: In this article, defect-rich Bi/Bi2O3 nanosheets in situ grown on the carbon fiber papers (Bi/Bi 2O3-CP) are directly used as an integrated cathode for CO2RR.
Abstract: Electrocatalytic reduction of CO2 to formate is believed as one of the most technologically and economically viable strategies for valuable fuels and chemical productions. Defect-rich Bi/Bi2O3 nanosheets in situ grown on the carbon fiber papers (Bi/Bi2O3-CP) are directly used as an integrated cathode for CO2RR. Bi/Bi2O3-CP exhibits a high mass-normalized formate partial current density of 32.4 and 50.7 mA∙mg−1 cm−2 at −0.87 and −0.97 V, respectively, with high formate faradic efficiency of about 90 %. Incredibly, this cathode gives a record mass-normalized formate production rate of 1.12 mmol∙mg-1 cm-2 h-1 at −1.17 V, which exceeds drop-casted sample (0.41 mmol∙mg−1 cm−-2 h−1 at −1.17 V) and most state-of-the-art Bi based electrocatalysts. The boosted formation generation could be attributed to the unique mesoporous 3D hierarchical nanostructure with the integrated contributions of abundant defects and synergistic coordination of regionally disordered Bi/Bi2O3 metal/oxide junction.
94 citations
TL;DR: In this paper, some up-to-date strategies in improving the CO2 reduction reaction (CO2RR) performance on carbon-based metal-free materials (CMs) are summarized.
75 citations
05 Apr 2019
TL;DR: In this paper, a mesoporous nanocrystals with abundant grain boundaries, high specific surface area, and easily accessible porosity result to be active and selective for the CO2 reduction reaction.
Abstract: In this Article, we present an easy, quick, and scalable route, based on anodic oxidation, for the preparation of mesoporous SnO2 as an efficient electrocatalyst for the CO2 reduction reaction (CO2RR). Crystallographically interconnected SnO2 nanocrystals with abundant grain boundaries, high specific surface area, and easily accessible porosity result to be active and selective for the CO2RR. This electrocatalyst shows faradaic efficiency (FE) of about 95% at −0.97 and −1.06 V versus reversible hydrogen electrode (RHE) toward the formation of predominant HCOOH and minor CO. A peak FE value of 82% for the HCOOH production is obtained at −1.06 V vs RHE. High HCOOH partial current densities of 10.2 and 15.3 mA cm–2 are observed at −0.97 and −1.15 V vs RHE, respectively. Thorough electrochemical characterizations demonstrate that the synthesized SnO2-based gas diffusion electrode allows efficient diffusion of CO2 even at high kinetics because of the highly open porous structure. The good understanding of the ...
60 citations
TL;DR: In this paper, the authors compared over 500 experimental data points from 65 scientific publications and patents and identified the gas diffusion electrode as the best technology to scale this reaction and identified critical areas where more research can provide crucial understandings to allow this technology to become a commercial process.
Abstract: The electrochemical reduction of carbon dioxide to formate is an appealing carbon utilization method as it can be performed at room temperature and pressure, it only requires two electrons, and it has a high atom efficiency. This reaction has been known and studied for decades, but currently there is no commercial process practiced. This Perspective compares over 500 experimental data points from 65 scientific publications and patents and identifies the gas diffusion electrode as the best technology to scale this reaction. We further discuss the complex layers that make up a gas diffusion electrode and view what has been studied with respect to this reaction. Finally, we identify critical areas where more research can provide crucial understandings to allow this technology to become a commercial process.
57 citations
References
More filters
TL;DR: This paper presents a probabilistic procedure for estimating the polymethine content of carbon dioxide using a straightforward two-step procedure, and shows good results in both the stationary and the liquid phase.
Abstract: Liming Dai,*,†,‡ Yuhua Xue,†,‡ Liangti Qu,* Hyun-Jung Choi, and Jong-Beom Baek* †Center of Advanced Science and Engineering for Carbon (Case4Carbon), Department of Macromolecular Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106, United States Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Department of Chemistry, School of Science, Beijing Institute of Technology, Beijing 100081, People’s Republic of China School of Energy and Chemical Engineering/Center for Dimension-Controllable Covalent Organic Frameworks, Ulsan National Institute of Science and Technology (UNIST), 100 Banyeon, Ulsan, 689-798, South Korea
1,967 citations
TL;DR: This tutorial review will present much of the significant work that has been done in the field of electrocatalytic and homogeneous reduction of carbon dioxide over the past three decades and extend the discussion to the important conclusions from previous work and recommendations for future directions to develop a catalytic system that will convert carbon dioxide to liquid fuels with high efficiencies.
Abstract: Research in the field of catalytic reduction of carbon dioxide to liquid fuels has grown rapidly in the past few decades. This is due to the increasing amount of carbon dioxide in the atmosphere and a steady climb in global fuel demand. This tutorial review will present much of the significant work that has been done in the field of electrocatalytic and homogeneous reduction of carbon dioxide over the past three decades. It will then extend the discussion to the important conclusions from previous work and recommendations for future directions to develop a catalytic system that will convert carbon dioxide to liquid fuels with high efficiencies.
1,688 citations
TL;DR: In this article, the product selectivity between CO and HCOO− has been investigated, which depends upon the combination of modifier atom and substrate electrode, and the order of CO selectivity agrees roughly with the electrode potential of CO2 reduction, and is rationalized in terms of stabilization of intermediate species CO−2 at the electrode surface.
1,564 citations
07 Mar 2008
TL;DR: In this article, the authors defined the energy conversion efficiency, defined as the ratio of the free energy of the products obtained in electrochemical CO2 reduction and that consumed in the reduction, would be roughly 30 to 40%.
Abstract: Carbon dioxide is a potential carbon resource abundant on earth. It is also a green house gas with a rapidly increasing atmospheric concentration during the last two centuries. Chemical fixation of CO2 is an attractive technique for utilization of carbon resources, as well as for the reduction of the atmospheric concentration of CO2. Nevertheless, CO2 is the stablest among carbon based substances under the environmental conditions. It has not been incorporated as a major industrial material. Carbon dioxide can be electrochemically reduced to useful products under mild conditions. However, the energy conversion efficiency, defined as the ratio of the free energy of the products obtained in electrochemical CO2 reduction and that consumed in the reduction, would be roughly 30 to 40%. 2 Such a low efficiency may discourage practical application of CO2 reduction in the very near future. However, the significance of the CO2 reduc-
1,381 citations
TL;DR: Electrokinetic studies indicate that the improved catalysis is linked to dramatically increased stabilization of the CO(2)(•-) intermediate on the surfaces of the oxide-derived Au electrodes.
Abstract: Carbon dioxide reduction is an essential component of many prospective technologies for the renewable synthesis of carbon-containing fuels. Known catalysts for this reaction generally suffer from low energetic efficiency, poor product selectivity, and rapid deactivation. We show that the reduction of thick Au oxide films results in the formation of Au nanoparticles (“oxide-derived Au”) that exhibit highly selective CO2 reduction to CO in water at overpotentials as low as 140 mV and retain their activity for at least 8 h. Under identical conditions, polycrystalline Au electrodes and several other nanostructured Au electrodes prepared via alternative methods require at least 200 mV of additional overpotential to attain comparable CO2 reduction activity and rapidly lose their activity. Electrokinetic studies indicate that the improved catalysis is linked to dramatically increased stabilization of the CO2•– intermediate on the surfaces of the oxide-derived Au electrodes.
1,379 citations