Project description:In catalysis science stability is as crucial as activity and selectivity. Understanding the degradation pathways occurring during operation and developing mitigation strategies will eventually improve catalyst design, thus facilitating the translation of basic science to technological applications. Herein, we reveal the unique and general degradation mechanism of metallic nanocatalysts during electrochemical CO2 reduction, exemplified by different sized copper nanocubes. We follow their morphological evolution during operation and correlate it with the electrocatalytic performance. In contrast with the most common coalescence and dissolution/precipitation mechanisms, we find a potential-driven nanoclustering to be the predominant degradation pathway. Grand-potential density functional theory calculations confirm the role of the negative potential applied to reduce CO2 as the main driving force for the clustering. This study offers a novel outlook on future investigations of stability and degradation reaction mechanisms of nanocatalysts in electrochemical CO2 reduction and, more generally, in electroreduction reactions.
Project description:Generating syngas (H2 and CO mixture) from electrochemically reduced CO2 in an aqueous solution is one of the sustainable strategies utilizing atmospheric CO2 in value-added products. However, a conventional single-component metal catalyst, such as Ag, Au, or Zn, exhibits potential-dependent CO2 reduction selectivity, which could result in temporal variation of syngas composition and limit its use in large-scale electrochemical syngas production. Herein, we demonstrate the use of Ag nanowire (NW)/porous carbon sheet composite catalysts in the generation of syngas with tunable H2/CO ratios having a large potential window to resist power fluctuation. These Ag NW/carbon sheet composite catalysts have a potential window increased by 10 times for generating syngas with the proper H2/CO ratio (1.7-2.15) for the Fischer-Tropsch process and an increased syngas production rate of about 19 times compared to that of a Ag foil. Additionally, we tuned the H2/CO ratio from ∼2 to ∼10 by adjusting only the quantity of the Ag NWs under the given electrode potential. We believe that our Ag NW/carbon sheet composite provides new possibilities for designing electrode structures with a large potential window and controlled CO2 reduction products in aqueous solutions.
Project description:The electrochemical reduction of CO2 offers an elegant solution to the current energy crisis and carbon emission issues, but the catalytic efficiency for CO2 reduction is seriously restricted by the inherent scaling relations between the adsorption energies of intermediates. Herein, by combining the concept of single-atom catalysts and multiple active sites, we design heteronuclear dual-atom catalysts to break through the stubborn restriction of scaling relations on catalytic activity. Twenty-one kinds of heteronuclear transition-metal dimers are embedded in monolayer C2N as potential dual-atom catalysts. First-principles calculations reveal that by adjusting the components of dimers, the two metal atoms play the role of carbon adsorption sites and oxygen adsorption sites respectively, which results in the decoupling of adsorption energies of key intermediates. Free energy profiles demonstrate that CO2 can be efficiently reduced to CH4 on CuCr/C2N and CuMn/C2N with low limiting potentials of -0.37 V and -0.32 V, respectively. This study suggests that the introduction of multiple active sites into porous two-dimensional materials would provide a great possibility for breaking scaling relations to achieve efficient multi-intermediate electrocatalytic reactions.
Project description:Carbon-based single-atom catalysts (SACs) with well-defined and homogeneously dispersed metal-N4 moieties provide a great opportunity for CO2 reduction. However, controlling the binding strength of various reactive intermediates on catalyst surface is necessary to enhance the selectivity to a desired product, and it is still a challenge. In this work, the authors prepared Sn SACs consisting of atomically dispersed SnN3 O1 active sites supported on N-rich carbon matrix (Sn-NOC) for efficient electrochemical CO2 reduction. Contrary to the classic Sn-N4 configuration which gives HCOOH and H2 as the predominant products, Sn-NOC with asymmetric atomic interface of SnN3 O1 gives CO as the exclusive product. Experimental results and density functional theory calculations show that the atomic arrangement of SnN3 O1 reduces the activation energy for *COO and *COOH formation, while increasing energy barrier for HCOO* formation significantly, thereby facilitating CO2 -to-CO conversion and suppressing HCOOH production. This work provides a new way for enhancing the selectivity to a specific product by controlling individually the binding strength of each reactive intermediate on catalyst surface.
Project description:Production of syngas with tunable CO/H2 ratio from renewable resources is an ideal way to provide a carbon-neutral feedstock for liquid fuel production. Ag is a benchmark electrocatalysts for CO2-to-CO conversion but high overpotential limits the efficiency. We synthesize AgP2 nanocrystals (NCs) with a greater than 3-fold reduction in overpotential for electrochemical CO2-to-CO reduction compared to Ag and greatly enhanced stability. Density functional theory calculations reveal a significant energy barrier decrease in the formate intermediate formation step. In situ X-ray absorption spectroscopy (XAS) shows that a maximum Faradaic efficiency is achieved at an average silver valence state of +1.08 in AgP2 NCs. A photocathode consisting of a n+p-Si wafer coated with ultrathin Al2O3 and AgP2 NCs achieves an onset potential of 0.2 V vs. RHE for CO production and a partial photocurrent density for CO at -0.11 V vs. RHE (j-0.11, CO) of -3.2 mA cm-2.
Project description:Direct electrochemical reduction of CO2 to fuels and chemicals using renewable electricity has attracted significant attention partly due to the fundamental challenges related to reactivity and selectivity, and partly due to its importance for industrial CO2-consuming gas diffusion cathodes. Here, we present advances in the understanding of trends in the CO2 to CO electrocatalysis of metal- and nitrogen-doped porous carbons containing catalytically active M-N x moieties (M?=?Mn, Fe, Co, Ni, Cu). We investigate their intrinsic catalytic reactivity, CO turnover frequencies, CO faradaic efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts rival Au- and Ag-based catalysts. We model the catalytically active M-N x moieties using density functional theory and correlate the theoretical binding energies with the experiments to give reactivity-selectivity descriptors. This gives an atomic-scale mechanistic understanding of potential-dependent CO and hydrocarbon selectivity from the M-N x moieties and it provides predictive guidelines for the rational design of selective carbon-based CO2 reduction catalysts.Inexpensive and selective electrocatalysts for CO2 reduction hold promise for sustainable fuel production. Here, the authors report N-coordinated, non-noble metal-doped porous carbons as efficient and selective electrocatalysts for CO2 to CO conversion.
Project description:Electrochemical CO2 reduction to value-added chemicals/fuels provides a promising way to mitigate CO2 emission and alleviate energy shortage. CO2 -to-CO conversion involves only two-electron/proton transfer and thus is kinetically fast. Among the various developed CO2 -to-CO reduction electrocatalysts, transition metal/N-doped carbon (M-N-C) catalysts are attractive due to their low cost and high activity. In this work, recent progress on the development of M-N-C catalysts for electrochemical CO2 -to-CO conversion is reviewed in detail. The regulation of the active sites in M-N-C catalysts and their related adjustable electrocatalytic CO2 reduction performance is discussed. A visual performance comparison of M-N-C catalysts for CO2 reduction reaction (CO2 RR) reported over the recent years is given, which suggests that Ni and Fe-N-C catalysts are the most promising candidates for large-scale reduction of CO2 to produce CO. Finally, outlooks and challenges are proposed for future research of CO2 -to-CO conversion.
Project description:Single-atom catalysts (SACs) are promising candidates to catalyze electrochemical CO2 reduction (ECR) due to maximized atomic utilization. However, products are usually limited to CO instead of hydrocarbons or oxygenates due to unfavorable high energy barrier for further electron transfer on synthesized single atom catalytic sites. Here we report a novel partial-carbonization strategy to modify the electronic structures of center atoms on SACs for lowering the overall endothermic energy of key intermediates. A carbon-dots-based SAC margined with unique CuN2O2 sites was synthesized for the first time. The introduction of oxygen ligands brings remarkably high Faradaic efficiency (78%) and selectivity (99% of ECR products) for electrochemical converting CO2 to CH4 with current density of 40 mA·cm-2 in aqueous electrolytes, surpassing most reported SACs which stop at two-electron reduction. Theoretical calculations further revealed that the high selectivity and activity on CuN2O2 active sites are due to the proper elevated CH4 and H2 energy barrier and fine-tuned electronic structure of Cu active sites.
Project description:Among the possible products of CO2 electrochemical reduction, CO plays a unique and vital role, which can be an ideal feedstock for further reduction to C2+ products, and also the important component of syngas that can be used as feedstock for value-added chemicals and fuels. However, it is still a challenge to tune the CO selectivity on Cu electrode. Here we newly construct an ultrasound-assisted electrochemical method for CO2 reduction, which can tune the selectivity of CO2 to CO from less than 10% to >80% at -1.18 V versus (vs.) reversible hydrogen electrode (RHE). The partial current density of CO production is significantly improved by 15 times. By in-situ Raman study, the dominating factor for the improved CO production is attributed to the accelerated desorption of *CO intermediate. This work provides a facile method to tune the product selectivity in CO2 electrochemical reduction.
Project description:PdH-based catalysts hold promise for both CO2 reduction to CO and the hydrogen evolution reaction. Density functional theory is used to systematically screen for stability, activity, and selectivity of transition metal dopants in PdH. The transition metal elements Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Ag, Cd, Hf, Ta, W, and Re are doped into PdH(111) surface with six different doping configurations: single, dimer, triangle, parallelogram, island, and overlayer. We find that several dopants, such as Ti and Nb, have excellent predicted catalytic activity and CO2 selectivity compared to the pure PdH hydride. In addition, they display good stability due to their negative doping formation energy. The improved performance can be assigned to reaction intermediates forming two bonds consisting of one C-Metal and one O-Metal bond on the PdH surface, which break the scaling relations of intermediates, and thus have stronger HOCO* binding facilitating CO2 activation.