Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Stabilizing indium sulfide for CO₂ electroreduction to formate at high rate by zinc incorporation.

ABSTRACT: Recently developed solid-state catalysts can mediate carbon dioxide (CO₂) electroreduction to valuable products at high rates and selectivities. However, under commercially relevant current densities of > 200 milliamperes per square centimeter (mA cm^-2), catalysts often undergo particle agglomeration, active-phase change, and/or element dissolution, making the long-term operational stability a considerable challenge. Here we report an indium sulfide catalyst that is stabilized by adding zinc in the structure and shows dramatically improved stability. The obtained ZnIn₂S₄ catalyst can reduce CO₂ to formate with 99.3% Faradaic efficiency at 300 mA cm^-2 over 60 h of continuous operation without decay. By contrast, similarly synthesized indium sulfide without zinc participation deteriorates quickly under the same conditions. Combining experimental and theoretical studies, we unveil that the introduction of zinc largely enhances the covalency of In-S bonds, which "locks" sulfur-a catalytic site that can activate H₂O to react with CO₂, yielding HCOO* intermediates-from being dissolved during high-rate electrolysis.

SUBMITTER: Chi LP

PROVIDER: S-EPMC8492718 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Surface Oxygen Injection in Tin Disulfide Nanosheets for Efficient CO2 Electroreduction to Formate and Syngas.

Project description:Surface chemistry modification represents a promising strategy to tailor the adsorption and activation of reaction intermediates for enhancing activity. Herein, we designed a surface oxygen-injection strategy to tune the electronic structure of SnS2 nanosheets, which showed effectively enhanced electrocatalytic activity and selectivity of CO2 reduction to formate and syngas (CO and H2). The oxygen-injection SnS2 nanosheets exhibit a remarkable Faradaic efficiency of 91.6% for carbonaceous products with a current density of 24.1 mA cm-2 at -0.9 V vs RHE, including 83.2% for formate production and 16.5% for syngas with the CO/H2 ratio of 1:1. By operando X-ray absorption spectroscopy, we unravel the in situ surface oxygen doping into the matrix during reaction, thereby optimizing the Sn local electronic states. Operando synchrotron radiation infrared spectroscopy along with theoretical calculations further reveals that the surface oxygen doping facilitated the CO2 activation and enhanced the affinity for HCOO* species. This result demonstrates the potential strategy of surface oxygen injection for the rational design of advanced catalysts for CO2 electroreduction.

| S-EPMC8421506 | biostudies-literature

SrO-layer insertion in Ruddlesden-Popper Sn-based perovskite enables efficient CO2 electroreduction towards formate.

Project description:Tin (Sn)-based oxides have been proved to be promising catalysts for the electrochemical CO2 reduction reaction (CO2RR) to formate (HCOO-). However, their performance is limited by their reductive transformation into metallic derivatives during the cathodic reaction. This paper describes the catalytic chemistry of a Sr2SnO4 electrocatalyst with a Ruddlesden-Popper (RP) perovskite structure for the CO2RR. The Sr2SnO4 electrocatalyst exhibits a faradaic efficiency of 83.7% for HCOO- at -1.08 V vs. the reversible hydrogen electrode with stability for over 24 h. The insertion of the SrO-layer in the RP structure of Sr2SnO4 leads to a change in the filling status of the anti-bonding orbitals of the Sn active sites, which optimizes the binding energy of *OCHO and results in high selectivity for HCOO-. At the same time, the interlayer interaction between interfacial octahedral layers and the SrO-layers makes the crystalline structure stable during the CO2RR. This study would provide fundamental guidelines for the exploration of perovskite-based electrocatalysts to achieve consistently high selectivity in the CO2RR.

| S-EPMC9350668 | biostudies-literature

Promoting electrocatalytic CO2 reduction to formate via sulfur-boosting water activation on indium surfaces.

Project description:Electrocatalytic reduction of CO2 to fuels and chemicals is one of the most attractive routes for CO2 utilization. Current catalysts suffer from low faradaic efficiency of a CO2-reduction product at high current density (or reaction rate). Here, we report that a sulfur-doped indium catalyst exhibits high faradaic efficiency of formate (>85%) in a broad range of current density (25-100?mA cm-2) for electrocatalytic CO2 reduction in aqueous media. The formation rate of formate reaches 1449??mol h-1 cm-2 with 93% faradaic efficiency, the highest value reported to date. Our studies suggest that sulfur accelerates CO2 reduction by a unique mechanism. Sulfur enhances the activation of water, forming hydrogen species that can readily react with CO2 to produce formate. The promoting effect of chalcogen modifiers can be extended to other metal catalysts. This work offers a simple and useful strategy for designing both active and selective electrocatalysts for CO2 reduction.

| S-EPMC6385284 | biostudies-literature

Efficient CO2 electroreduction on facet-selective copper films with high conversion rate.

Project description:Tuning the facet exposure of Cu could promote the multi-carbon (C2+) products formation in electrocatalytic CO2 reduction. Here we report the design and realization of a dynamic deposition-etch-bombardment method for Cu(100) facets control without using capping agents and polymer binders. The synthesized Cu(100)-rich films lead to a high Faradaic efficiency of 86.5% and a full-cell electricity conversion efficiency of 36.5% towards C2+ products in a flow cell. By further scaling up the electrode into a 25 cm2 membrane electrode assembly system, the overall current can ramp up to 12 A while achieving a single-pass yield of 13.2% for C2+ products. An insight into the influence of Cu facets exposure on intermediates is provided by in situ spectroscopic methods supported by theoretical calculations. The collected information will enable the precise design of CO2 reduction reactions to obtain desired products, a step towards future industrial CO2 refineries.

| S-EPMC8484611 | biostudies-literature

Potential-Dependent Competitive Electroreduction of CO2 into CO and Formate on Cu(111) from an Improved H Coverage-Dependent Electrochemical Model with Explicit Solvent Effect.

Project description:An improved density functional theory-based H coverage-dependent electrochemical model with explicit solvent effect is proposed for Cu(111), which is used to identify potential-dependent initial competitive CO2 electroreduction pathways considering HER. We find that a chemisorbed CO2 molecule at the present electrode/aqueous interface can be spontaneously formed and the overpotentials can affect its coordination pattern. The Eley-Rideal mechanism may be more favorable during the initial CO2 electroreduction into CO, whereas chemisorbed CO2 reacting with adsorbed H into HCOO- via the Langmuir-Hinshelwood mechanism is more facile to occur. The analyses of energetics suggest that the low overpotentials have a negligible influence on CO and HCOO- formation, and HCOO- species with monodentate and bidentate configurations may also parallelly form with the surmountable barriers at room temperature. However, the high potentials have an interruptive effect on initial CO2 electroreduction because of the significantly increased barriers, indicating that the chemisorbed CO2 can be stabilized by imposing more negative potentials and thus going against initial CO2 electroreduction. By analyzing the competing HER with initial CO2 electroreduction into CO, we find that HER is competitive with initial CO formation because of the required lower overpotentials. Simultaneously, the present study shows that the blocked Cu surface by adsorbed H and CO can explain why the initial CO formation pathway is unfavorable at the high overpotentials. Our present conclusions can also confirm the previous experimental report on initial formation of CO and HCOO-.

| S-EPMC7288361 | biostudies-literature

Copper Carbonate Hydroxide as Precursor of Interfacial CO in CO2 Electroreduction.

Project description:Copper electrodes are especially effective in catalysis of C2 and further multi-carbon products in the CO2 reduction reaction (CO2 RR) and therefore of major technological interest. The reasons for the unparalleled Cu performance in CO2 RR are insufficiently understood. Here, the electrode-electrolyte interface was highlighted as a dynamic physical-chemical system and determinant of catalytic events. Exploiting the intrinsic surface-enhanced Raman effect of previously characterized Cu foam electrodes, operando Raman experiments were used to interrogate structures and molecular interactions at the electrode-electrolyte interface at subcatalytic and catalytic potentials. Formation of a copper carbonate hydroxide (CuCarHyd) was detected, which resembles the mineral malachite. Its carbonate ions could be directly converted to CO at low overpotential. These and further experiments suggested a basic mode of CO2 /carbonate reduction at Cu electrodes interfaces that contrasted previous mechanistic models: the starting point in carbon reduction was not CO2 but carbonate ions bound to the metallic Cu electrode in form of CuCarHyd structures. It was hypothesized that Cu oxides residues could enhance CO2 RR indirectly by supporting formation of CuCarHyd motifs. The presence of CuCarHyd patches at catalytic potentials might result from alkalization in conjunction with local electrical potential gradients, enabling the formation of metastable CuCarHyd motifs over a large range of potentials.

| S-EPMC9314821 | biostudies-literature

Carbon-supported Ni nanoparticles for efficient CO2 electroreduction.

Project description:The development of highly selective, low cost, and energy-efficient electrocatalysts is crucial for CO2 electrocatalysis to mitigate energy shortages and to lower the global carbon footprint. Herein, we first report that carbon-coated Ni nanoparticles supported on N-doped carbon enable efficient electroreduction of CO2 to CO. In contrast to most previously reported Ni metal catalysts that resulted in severe hydrogen evolution during CO2 conversion, the Ni particle catalyst here presents an unprecedented CO faradaic efficiency of approximately 94% at an overpotential of 0.59 V, even comparable to that of the best single Ni sites. The catalyst also affords a high CO partial current density and a large CO turnover frequency, reaching 22.7 mA cm-2 and 697 h-1 at -1.1 V (versus the reversible hydrogen electrode), respectively. Experiments combined with density functional theory calculations showed that the carbon layer coated on Ni and N-dopants in carbon material both play important roles in improving catalytic activity for electrochemical CO2 reduction to CO by stabilizing *COOH without affecting the easy *CO desorption ability of the catalyst.

| S-EPMC6335639 | biostudies-literature

Iodide-mediated Cu catalyst restructuring during CO2 electroreduction.

Project description:Catalyst restructuring during electrochemical reactions is a critical but poorly understood process that determines the underlying structure-property relationships during catalysis. In the electrocatalytic reduction of CO2 (CO2RR), it is known that Cu, the most favorable catalyst for hydrocarbon generation, is highly susceptible to restructuring in the presence of halides. Iodide ions, in particular, greatly improved the catalyst performance of Cu foils, although a detailed understanding of the morphological evolution induced by iodide remains lacking. It is also unclear if a similar enhancement transfers to catalyst particles. Here, we first demonstrate that iodide pre-treatment improves the selectivity of hexagonally ordered Cu-island arrays towards ethylene and oxygenate products. Then, the morphological changes in these arrays caused by iodide treatment and during CO2RR are visualized using electrochemical transmission electron microscopy. Our observations reveal that the Cu islands evolve into tetrahedral CuI, which then become 3-dimensional chains of copper nanoparticles under CO2RR conditions. Furthermore, CuI and Cu2O particles re-precipitated when the samples are returned to open circuit potential, implying that iodide and Cu+ species are present within these chains. This work provides detailed insight into the role of iodide, and its impact on the prevailing morphologies that exist during CO2RR.

| S-EPMC9255670 | biostudies-literature

Plasma-Modified Dendritic Cu Catalyst for CO2 Electroreduction.

Project description:Efficient and active catalysts with high selectivity for hydrocarbons and other valuable chemicals during stable operation are crucial. We have taken advantage of low-pressure oxygen plasmas to modify dendritic Cu catalysts and were able to achieve enhanced selectivity toward C2 and C3 products. Utilizing operando spectroscopic methods such as X-ray absorption fine-structure spectroscopy (XAFS) and quasi in situ X-ray photoelectron spectroscopy (XPS), we observed that the initial presence of oxides in these catalysts before the reaction plays an inferior role in determining their catalytic performance as compared to the overall catalyst morphology. This is assigned to the poor stability of the Cu x O species in these materials under the conditions of electrocatalytic conversion of CO2 (CO2RR). Our findings shed light into the strong structure/chemical state-selectivity correlation in CO2RR and open venues for the rational design of more effective catalysts through plasma pretreatments.

| S-EPMC6559126 | biostudies-literature

Efficient wettability-controlled electroreduction of CO2 to CO at Au/C interfaces.

Project description:The electrochemical CO2 reduction reaction (CO2RR) represents a very promising future strategy for synthesizing carbon-containing chemicals in a more sustainable way. In spite of great progress in electrocatalyst design over the last decade, the critical role of wettability-controlled interfacial structures for CO2RR remains largely unexplored. Here, we systematically modify the structure of gas-liquid-solid interfaces over a typical Au/C gas diffusion electrode through wettability modification to reveal its contribution to interfacial CO2 transportation and electroreduction. Based on confocal laser scanning microscopy measurements, the Cassie-Wenzel coexistence state is demonstrated to be the ideal three phase structure for continuous CO2 supply from gas phase to Au active sites at high current densities. The pivotal role of interfacial structure for the stabilization of the interfacial CO2 concentration during CO2RR is quantitatively analysed through a newly-developed in-situ fluorescence electrochemical spectroscopic method, pinpointing the necessary CO2 mass transfer conditions for CO2RR operation at high current densities.

| S-EPMC7295780 | biostudies-literature