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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

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

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

A bioinspired molybdenum-copper molecular catalyst for CO2 electroreduction.

Project description:Non-noble metal molecular catalysts mediating the electrocatalytic reduction of carbon dioxide are still scarce. This work reports the electrochemical reduction of CO2 to formate catalyzed by the bimetallic complex [(bdt)MoVI(O)S2CuICN]2- (bdt = benzenedithiolate), a mimic of the active site of the Mo-Cu carbon monoxide dehydrogenase enzyme (CODH2). Infrared spectroelectrochemical (IR-SEC) studies coupled with density functional theory (DFT) computations revealed that the complex is only a pre-catalyst, the active catalyst being generated upon reduction in the presence of CO2. We found that the two-electron reduction of [(bdt)MoVI(O)S2CuICN]2- triggers the transfer of the oxo moiety to CO2 forming CO3 2- and the complex [(bdt)MoIVS2CuICN]2- and that a further one-electron reduction is needed to generate the active catalyst. Its protonation yields a reactive MoVH hydride intermediate which reacts with CO2 to produce formate. These findings are particularly relevant to the design of catalysts from metal oxo precursors.

| S-EPMC7448372 | biostudies-literature

A high-performance oxygen evolution catalyst in neutral-pH for sunlight-driven CO2 reduction.

Project description:The efficiency of sunlight-driven reduction of carbon dioxide (CO2), a process mimicking the photosynthesis in nature that integrates the light harvester and electrolysis cell to convert CO2 into valuable chemicals, is greatly limited by the sluggish kinetics of oxygen evolution in pH-neutral conditions. Current non-noble metal oxide catalysts developed to drive oxygen evolution in alkaline solution have poor performance in neutral solutions. Here we report a highly active and stable oxygen evolution catalyst in neutral pH, Brownmillerite Sr2GaCoO5, with the specific activity about one order of magnitude higher than that of widely used iridium oxide catalyst. Using Sr2GaCoO5 to catalyze oxygen evolution, the integrated CO2 reduction achieves the average solar-to-CO efficiency of 13.9% with no appreciable performance degradation in 19 h of operation. Our results not only set a record for the efficiency in sunlight-driven CO2 reduction, but open new opportunities towards the realization of practical CO2 reduction systems.

| S-EPMC6733866 | biostudies-literature

Probing the local activity of CO2 reduction on gold gas diffusion electrodes: effect of the catalyst loading and CO2 pressure.

Project description:Large scale CO2 electrolysis can be achieved using gas diffusion electrodes (GDEs), and is an essential step towards broader implementation of carbon capture and utilization strategies. Different variables are known to affect the performance of GDEs. Especially regarding the catalyst loading, there are diverging trends reported in terms of activity and selectivity, e.g. for CO2 reduction to CO. We have used shear-force based Au nanoelectrode positioning and scanning electrochemical microscopy (SECM) in the surface-generation tip collection mode to evaluate the activity of Au GDEs for CO2 reduction as a function of catalyst loading and CO2 back pressure. Using a Au nanoelectrode, we have locally measured the amount of CO produced along a catalyst loading gradient under operando conditions. We observed that an optimum local loading of catalyst is necessary to achieve high activities. However, this optimum is directly dependent on the CO2 back pressure. Our work does not only present a tool to evaluate the activity of GDEs locally, it also allows drawing a more precise picture regarding the effect of catalyst loading and CO2 back pressure on their performance.

| S-EPMC8654039 | biostudies-literature

Protonation of the dinitrogen-reduction catalyst [HIPTN3N]Mo(III) investigated by ENDOR spectroscopy.

Project description:Dinitrogen is reduced to ammonia by the molybdenum complex of L = [HIPTN3N](3-) [Mo; HIPT = 3,5-(2,4,6-iPr3C6H2)2C6H3]. The mechanism by which this occurs involves the stepwise addition of proton/electron pairs, but how the first pair converts MoN2 to MoN ? NH remains uncertain. The first proton of reduction might bind either at N? of N2 or at one of the three amido nitrogen (N(am)) ligands. Treatment of MoCO with [2,4,6-Me3C5H3N]BAr'4 [Ar' = 2,3-(CF3)2C6H3] in the absence of reductant generates HMoCO(+), whose electron paramagnetic resonance spectrum has greatly reduced g anisotropy relative to MoCO. (2)H Mims pulsed electron nuclear double-resonance spectroscopy of (2)HMoCO(+) shows a signal that simulations show to have a hyperfine tensor with an isotropic coupling, aiso((2)H) = -0.22 MHz, and a roughly dipolar anisotropic interaction, T((2)H) = [-0.48, -0.93, 1.42] MHz. The simulations show that the deuteron is bound to N(am), near the Mo equatorial plane, not along the normal, and at a distance of 2.6 Å from Mo, which is nearly identical with the (Nam)(2)H(+)-Mo distance predicted by density functional theory computations.

| S-EPMC3139016 | biostudies-literature

Performance of a NiFe2O4@Co Core-Shell Fischer-Tropsch Catalyst: Effect of Low Temperature Reduction.

Project description:In situ TEM gas-cell imaging and spectroscopy with in situ XRD have been applied to reveal morphological changes in NiFe2O4@Co3O4 core-shell nanoparticles in hydrogen. The core-shell structure is retained upon reduction under mild conditions (180 °C for 1 h), resulting in a partially reduced shell. The core-shell structure was retained after exposing these reduced NiFe2O4@Co3O4 core-shell nanoparticles to Fischer-Tropsch conditions at 230 °C and 20 bar. Slightly harsher reduction (230 °C, 2 h) resulted in restructuring of the NiFe2O4@Co3O4 core-shell nanoparticles to form cobalt islands in addition to partially reduced NiFe2O4. NiFe2O4 underwent further transformation upon exposure to Fischer-Tropsch conditions, resulting in the formation of iron carbide and nickel/iron-nickel alloy. The turnover frequency in the Fischer-Tropsch synthesis over NiFe2O4@Co3O4 core-shell nanoparticles reduced in hydrogen at 180 °C for 1 h was estimated to be less than 0.02 s-1 (cobalt-time yield of 8.40 μmol.g-1.s-1) with a C5+ selectivity of 38 C-%. The low turnover frequency under these conditions in relation to the turnover frequency obtained with unsupported cobalt is attributed to the strain in the catalytically active cobalt.

| S-EPMC7774086 | biostudies-literature

Low temperature methanation of CO2 over an amorphous cobalt-based catalyst.

Project description:CO2 methanation is an important reaction in CO2 valorization. Because of the high kinetic barriers, the reaction usually needs to proceed at higher temperature (>300 °C). High-efficiency CO2 methanation at low temperature (<200 °C) is an interesting topic, and only several noble metal catalysts were reported to achieve this goal. Currently, design of cheap metal catalysts that can effectively accelerate this reaction at low temperature is still a challenge. In this work, we found that the amorphous Co-Zr0.1-B-O catalyst could catalyze the reaction at above 140 °C. The activity of the catalyst at 180 °C reached 10.7 mmolCO2 gcat -1 h-1, which is comparable to or even higher than that of some noble metal catalysts under similar conditions. The Zr promoter in this work had the highest promoting factor to date among the catalysts for CO2 methanation. As far as we know, this is the first report of an amorphous transition metal catalyst that could effectively accelerate CO2 methanation. The outstanding performance of the catalyst could be ascribed to two aspects. The amorphous nature of the catalyst offered abundant surface defects and intrinsic active sites. On the other hand, the Zr promoter could enlarge the surface area of the catalyst, enrich the Co atoms on the catalyst surface, and tune the valence state of the atoms at the catalyst surface. The reaction mechanism was proposed based on the control experiments.

| S-EPMC8179427 | biostudies-literature

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