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A Molecular CO₂ Reduction Catalyst Based on Giant Polyoxometalate {Mo₃₆₈}.

ABSTRACT: Photocatalytic CO₂ reduction in water is one of the most attractive research pursuits of our time. In this article we report a giant polyoxometalate {Mo₃₆₈} based homogeneous catalytic system, which efficiently reduces CO₂ to formic acid with a maximum turnover number (TON) of 27,666, turnover frequency (TOF) of 4,611 h^-1 and external quantum efficiency of the reaction is 0.6%. The catalytic system oxidizes water and releases electrons, and these electrons are further utilized for the reduction of CO₂ to formic acid. A maximum of 8.3 mmol of formic acid was observed with the loading of 0.3 μmol of the catalyst. Our catalyst material is also stable throughout the reaction. The starting materials for this experiment are CO₂ and H₂O and the end products are HCOOH and O₂. The formic acid formed in this reaction is an important H₂ gas carrier and thus significant in renewable energy research.

SUBMITTER: Das S

PROVIDER: S-EPMC6224680 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Corrigendum: A Molecular CO2 Reduction Catalyst Based on Giant Polyoxometalate {Mo368}.

Project description:[This corrects the article DOI: 10.3389/fchem.2018.00514.].

| S-EPMC8264779 | biostudies-literature

Pd-incorporated polyoxometalate catalysts for electrochemical CO2 reduction.

Project description:Polyoxometalates (POMs), representing anionic metal-oxo clusters, display diverse properties depending on their structures, constituent elements, and countercations. These characteristics position them as promising catalysts or catalyst precursors for electrochemical carbon dioxide reduction reaction (CO2RR). This study synthesized various salts-TBA+ (tetra-n-butylammonium), Cs+, Sr2+, and Ba2+-of a dipalladium-incorporated POM (Pd2, [γ-H2SiW10O36Pd2(OAc)2]4-) immobilized on a carbon support (Pd2/C). The synthesized catalysts-TBAPd2/C, CsPd2/C, SrPd2/C, and BaPd2/C-were deposited on a gas-diffusion carbon electrode, and the CO2RR performance was subsequently evaluated using a gas-diffusion flow electrolysis cell. Among the catalysts tested, BaPd2/C exhibited high selectivity toward carbon monoxide (CO) production (ca. 90%), while TBAPd2/C produced CO and hydrogen (H2) with moderate selectivity (ca. 40% for CO and ca. 60% for H2). Moreover, BaPd2/C exhibited high selectivity toward CO production over 12 h, while palladium acetate, a precursor of Pd2, showed a significant decline in CO selectivity during the CO2RR. Although both BaPd2/C and TBAPd2/C transformed into Pd nanoparticles and WO x nanospecies during the CO2RR, the influence of countercations on their product selectivity was significant. These results highlight that POMs and their countercations can effectively modulate the catalytic performance of POM-based electrocatalysts in CO2RR.

| S-EPMC11342151 | biostudies-literature

Exploring the Molecular Growth of Two Gigantic Half-Closed Polyoxometalate Clusters {Mo180 } and {Mo130 Ce6 }.

Project description:Understanding the process of the self-assembly of gigantic polyoxometalates and their subsequent molecular growth, by the addition of capping moieties onto the oxo-frameworks, is critical for the development of the designed assembly of complex high-nuclearity cluster species, yet such processes remain far from being understood. Herein we describe the molecular growth from {Mo150 } and {Mo120 Ce6 } to afford two half-closed gigantic molybdenum blue clusters {Mo180 } (1) and {Mo130 Ce6 } (2), respectively. Compound 1 features a hat-shaped structure with the parent wheel-shaped {Mo150 } being capped by a {Mo30 } unit on one side. Similarly, 2 exhibits an elliptical lanthanide-doped wheel {Mo120 Ce6 } that is sealed by a {Mo10 } unit on one side. Moreover, the observation of the parent uncapped {Mo150 } and {Mo120 Ce6 } clusters as minor products during the synthesis of 1 and 2 strongly suggests that the molecular growth process can be initialized from {Mo150 } and {Mo120 Ce6 } in solution, respectively.

| S-EPMC5600119 | biostudies-literature

Electrochemical Water Oxidation and CO2 Reduction with a Nickel Molecular Catalyst.

Project description:Mimicking the photosynthesis of green plants to combine water oxidation with CO2 reduction is of great significance for solving energy and environmental crises. In this context, a trinuclear nickel complex, [NiII3(paoH)6(PhPO3)2]·2ClO4 (1), with a novel structure has been constructed with PhPO32- (phenylphosphonate) and paoH (2-pyridine formaldehyde oxime) ligands and possesses a reflection symmetry with a mirror plane revealed by single-crystal X-ray diffraction. Bulk electrocatalysis demonstrates that complex 1 can homogeneously catalyze water oxidation and CO2 reduction simultaneously. It can catalyze water oxidation at a near-neutral condition of pH = 7.45 with a high TOF of 12.2 s-1, and the Faraday efficiency is as high as 95%. Meanwhile, it also exhibits high electrocatalytic activity for CO2 reduction towards CO with a TOF of 7.84 s-1 in DMF solution. The excellent electrocatalytic performance of the water oxidation and CO2 reduction of complex 1 could be attributed to the two unique µ3-PhPO32- bridges as the crucial factor for stabilizing the trinuclear molecule as well as the proton transformation during the catalytic process, while the oxime groups modulate the electronic structure of the metal centers via π back-bonding. Therefore, apart from the cooperation effect of the three Ni centers for catalysis, simultaneously, the two kinds of ligands in complex 1 can also synergistically coordinate the central metal, thereby significantly promoting its catalytic performance. Complex 1 represents the first nickel molecular electrocatalyst for both water oxidation and CO2 reduction. The findings in this work open an avenue for designing efficient molecular electrocatalysts with peculiar ligands.

| S-EPMC10856054 | biostudies-literature

Ce-mediated molecular tailoring on gigantic polyoxometalate {Mo132} into half-closed {Ce11Mo96} for high proton conduction.

Project description:Precise synthesis of polyoxometalates (POMs) is important for the fundamental understanding of the relationship between the structure and function of each building motif. However, it is a great challenge to realize the atomic-level tailoring of specific sites in POMs without altering the major framework. Herein, we report the case of Ce-mediated molecular tailoring on gigantic {Mo132}, which has a closed structural motif involving a never seen {Mo110} decamer. Such capped wheel {Mo132} undergoes a quasi-isomerism with known {Mo132} ball displaying different optical behaviors. Experiencing an 'Inner-On-Outer' binding process with the substituent of {Mo2} reactive sites in {Mo132}, the site-specific Ce ions drive the dissociation of {Mo2*} clipping sites and finally give rise to a predictable half-closed product {Ce11Mo96}. By virtue of the tailor-made open cavity, the {Ce11Mo96} achieves high proton conduction, nearly two orders of magnitude than that of {Mo132}. This work offers a significant step toward the controllable assembly of POM clusters through a Ce-mediated molecular tailoring process for desirable properties.

| S-EPMC10439156 | biostudies-literature

A donor-chromophore-catalyst assembly for solar CO2 reduction.

Project description:We describe here the preparation and characterization of a photocathode assembly for CO2 reduction to CO in 0.1 M LiClO4 acetonitrile. The assembly was formed on 1.0 μm thick mesoporous films of NiO using a layer-by-layer procedure based on Zr(iv)-phosphonate bridging units. The structure of the Zr(iv) bridged assembly, abbreviated as NiO|-DA-RuCP2 2+-Re(i), where DA is the dianiline-based electron donor (N,N,N',N'-((CH2)3PO3H2)4-4,4'-dianiline), RuCP2+ is the light absorber [Ru((4,4'-(PO3H2CH2)2-2,2'-bipyridine)(2,2'-bipyridine))2]2+, and Re(i) is the CO2 reduction catalyst, ReI((4,4'-PO3H2CH2)2-2,2'-bipyridine)(CO)3Cl. Visible light excitation of the assembly in CO2 saturated solution resulted in CO2 reduction to CO. A steady-state photocurrent density of 65 μA cm-2 was achieved under one sun illumination and an IPCE value of 1.9% was obtained with 450 nm illumination. The importance of the DA aniline donor in the assembly as an initial site for reduction of the RuCP2+ excited state was demonstrated by an 8 times higher photocurrent generated with DA present in the surface film compared to a control without DA. Nanosecond transient absorption measurements showed that the expected reduced one-electron intermediate, RuCP+, was formed on a sub-nanosecond time scale with back electron transfer to the electrode on the microsecond timescale which competes with forward electron transfer to the Re(i) catalyst at t 1/2 = 2.6 μs (k ET = 2.7 × 105 s-1).

| S-EPMC6482438 | biostudies-literature

Two-dimensional molybdenum carbide 2D-Mo2C as a superior catalyst for CO2 hydrogenation.

Project description:Early transitional metal carbides are promising catalysts for hydrogenation of CO2. Here, a two-dimensional (2D) multilayered 2D-Mo2C material is prepared from Mo2CTx of the MXene family. Surface termination groups Tx (O, OH, and F) are reductively de-functionalized in Mo2CTx (500 °C, pure H2) avoiding the formation of a 3D carbide structure. CO2 hydrogenation studies show that the activity and product selectivity (CO, CH4, C2-C5 alkanes, methanol, and dimethyl ether) of Mo2CTx and 2D-Mo2C are controlled by the surface coverage of Tx groups that are tunable by the H2 pretreatment conditions. 2D-Mo2C contains no Tx groups and outperforms Mo2CTx, β-Mo2C, or the industrial Cu-ZnO-Al2O3 catalyst in CO2 hydrogenation (evaluated by CO weight time yield at 430 °C and 1 bar). We show that the lack of surface termination groups drives the selectivity and activity of Mo-terminated carbidic surfaces in CO2 hydrogenation.

| S-EPMC8448824 | biostudies-literature

Facet-specific Active Surface Regulation of Bix MOy (M=Mo, V, W) Nanosheets for Boosted Photocatalytic CO2 reduction.

Project description:Photocatalytic performance can be optimized via introduction of reactive sites. However, it is practically difficult to engineer these on specific photocatalyst surfaces, because of limited understanding of atomic-level structure-activity. Here we report a facile sonication-assisted chemical reduction for specific facets regulation via oxygen deprivation on Bi-based photocatalysts. The modified Bi2 MoO6 nanosheets exhibit 61.5 and 12.4 μmol g-1 for CO and CH4 production respectively, ≈3 times greater than for pristine catalyst, together with excellent stability/reproducibility of ≈20 h. By combining advanced characterizations and simulation, we confirm the reaction mechanism on surface-regulated photocatalysts, namely, induced defects on highly-active surface accelerate charge separation/transfer and lower the energy barrier for surface CO2 adsorption/activation/reduction. Promisingly, this method appears generalizable to a wider range of materials.

| S-EPMC10100506 | biostudies-literature

Mo2C-induced hydrogen production enhances microbial electrosynthesis of acetate from CO2 reduction.

Project description:BackgroundMicrobial electrosynthesis (MES) is a biocathode-driven process, in which electroautotrophic microorganisms can directly uptake electrons or indirectly via H2 from the cathode as energy sources and CO2 as only carbon source to produce chemicals.ResultsThis study demonstrates that a hydrogen evolution reaction (HER) catalyst can enhance MES performance. An active HER electrocatalyst molybdenum carbide (Mo2C)-modified electrode was constructed for MES. The volumetric acetate production rate of MES with 12 mg cm-2 Mo2C was 0.19 ± 0.02 g L-1 day-1, which was 2.1 times higher than that of the control. The final acetate concentration reached 5.72 ± 0.6 g L-1 within 30 days, and coulombic efficiencies of 64 ± 0.7% were yielded. Furthermore, electrochemical study, scanning electron microscopy, and microbial community analyses suggested that Mo2C can accelerate the release of hydrogen, promote the formation of biofilms and regulate the mixed microbial flora.ConclusionCoupling a HER catalyst to a cathode of MES system is a promising strategy for improving MES efficiency.

| S-EPMC6442412 | biostudies-literature

Selectivity control towards CO versus H2 for photo-driven CO2 reduction with a novel Co(II) catalyst.

Project description:Developing efficient catalysts for reducing carbon dioxide, a highly stable combustion waste product, is a relevant task to lower the atmospheric concentration of this greenhouse gas by upcycling. Selectivity towards CO2-reduction products is highly desirable, although it can be challenging to achieve since the metal-hydrides formation is sometimes favored and leads to H2 evolution. In this work, we designed a cobalt-based catalyst, and we present herein its physicochemical properties. Moreover, we tailored a fully earth-abundant photocatalytic system to achieve specifically CO2 reduction, optimizing efficiency and selectivity. By changing the conditions, we enhanced the turnover number (TON) of CO production from only 0.5 to more than 60 and the selectivity from 6% to 97% after four hours of irradiation at 420 nm. Further efficiency enhancement was achieved by adding 1,1,1,3,3,3-hexafluoropropan-2-ol, producing CO with a TON up to 230, although at the expense of selectivity (54%).

| S-EPMC10667713 | biostudies-literature

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