CH4 Oxidation Research Articles

Tailoring Pd/M@CoAlO core-shell catalyst morphology for efficient methane oxidation

The control of low-concentration methane (CH4) emissions is a critical component of the ‘dual carbon’ strategy, and catalytic combustion technology focused on catalyst design is recognized as a promising avenue for achieving it. However, the zeolite-based catalysts are highly prone to deactivation under hydrothermal environments, thus limiting their practical applicability. Herein, we have utilized layered double hydroxides (LDHs) as precursors and integrated them with Pd/M through a co-precipitation method to fabricate Pd/M@CoAlO composite catalysts with a core–shell structure, focused on the impact of CoAlO morphology on the activity and stability for CH4 oxidation. It revealed that the incorporation of CoAlO significantly enhanced the catalytic combustion efficiency and the hydrothermal stability of Pd/M. Furthermore, an increase in the calcination temperature led to a progressive degradation of the sheet-like or petal-shaped structure of CoAlO within the Pd/M@CoAlO composite catalysts. This structural collapse eventually resulted in the formation of CoAlO dense particles that enveloped the Pd/M, adversely affecting the adsorption of oxygen and the exposure of active sites. This work underscores the importance of morphological control, providing significant guidance for the strategic design and development of catalysts tailored for CH4 catalytic combustion.

Global Wetland Methane Emissions From 2001 to 2020: Magnitude, Dynamics and Controls

AbstractThe large uncertainties in estimating CH4 emissions from wetland ecosystems, the leading natural source to the atmosphere, substantially hinder the quantification of the global CH4 budget. This study used the IBIS‐CH4 (Integrated BIosphere Simulator‐Methane) model, a process‐based model integrating microbial mechanisms associated with CH4 production and oxidation processes, to simulate global wetland CH4 emissions from 2001 to 2020. Initially, we employed the IBIS‐CH4 model to evaluate its performance across 26 diverse wetland sites worldwide. The results showed that the magnitude and seasonality of observed CH4 fluxes over various wetland sites were well reproduced. We then used this model to estimate the annual global wetland CH4 emissions from 2001 to 2020, averaging 152.67 Tg CH4 yr−1, with a range of 135.72–167.57 Tg CH4 yr−1. The estimated global wetland CH4 emissions are generally in agreement with the current bottom‐up estimates (117–256 Tg CH4 yr−1) and closely overlap with independent top‐down estimates (139–183 Tg CH4 yr−1). During 2001–2020, the estimated global wetland CH4 emissions initially showed an increasing trend, followed by a decline. The peak of CH4 emissions reached in 2010, coinciding with the peak of wetland area. The majority of global wetland CH4 emissions were concentrated in tropical regions, which exhibited a clear seasonality and had a peak in July. The impact of meteorological factors on wetland CH4 emissions was greater than that of leaf area index, indicating the importance of soil hydrothermal conditions on wetland CH4 emissions.

Selectively photocatalytic oxidation of methane to methanol promoted by Charge-Polarized Zn-Ti pairs

Photocatalysis offers an intriguing route for selective oxidation of CH4 to CH3OH under mild conditions. However, owing to the ultra-high stability of CH4 and the diversity of oxidative products, the activity of CH4 oxidation and the selectivity of CH3OH are still far from satisfactory. Herein, we report a dual-cocatalyst of Au and bimetallic oxide (Zn2Ti3O8) nanoparticles (NPs) modified TiO2 nanotube (Au/Zn2Ti3O8/TiO2) for highly active and selective photocatalytic oxidation of CH4 to CH3OH with O2 at room temperature. The introduction of Zn2Ti3O8 NPs is skillfully exploited the epitaxies of ZIF-8 on the surface of protonated titanate nanotubes (H-TNTs) and the followed thermal treatment with air. During photocatalytic CH4 oxidation, 1.7 %Au/Zn2Ti3O8/TiO2-4 achieved a formation rate of liquid oxygenates of 1200 μmol·gcat.–1·h−1 with a CH3OH selectivity of 91.5 %, which were much higher than those over 1.7 %Au/TiO2 and 1.7 %Au/ZnO. Mechanism investigation confirmed the presence of the strong electron interaction between Au NPs, Zn2Ti3O8 NPs and TiO2 nanotubes in 1.7 %Au/Zn2Ti3O8/TiO2-4, which intensified the charge polarization between Zn sites and Ti sites. These charge-polarized Zn-Ti sites were not only beneficial to the adsorption and activation of CH4, but also accelerated the further transformation of CH3OOH to CH3OH, as well as inhibited the excessive oxidation of CH3OH.

Impacts of O2:CH4 ratios and CH4 concentrations on the denitrification and CH4 oxidations of a novel AME-AD system

Aerobic methane (CH4) oxidation coupled to denitrification (AME-D) is a promising process for the denitrification of low C/N wastewater. Compared with anaerobic denitrifying bacteria, aerobic denitrifying bacteria may enable AME-D have high denitrification ability under aerobic conditions. This study constructed a novel aerobic methane oxidation coupled to aerobic denitrification (AME-AD) system using the typical aerobic denitrifying bacteria Paracoccus pantotrophus ATCC35512 and the typical aerobic methane oxidizing bacteria Methylosinus trichosporium OB3b. The denitrification and CH4 oxidations of AME-AD with different O2:CH4 ratios (0:1, 0.25:1, 0.5:1, 0.75:1, 1:1 and 1.25:1) and CH4 concentrations (0, 14000, 28000, 42000, 56000 and 70000 mg m−3) were investigated in batch experiments. Higher O2:CH4 ratios can significantly improve the denitrification and CH4 oxidations of the AME-AD (P < 0.05). The treatment with an O2:CH4 ratio of 1.25:1 had the highest denitrification rate (0.036 mg h−1) and highest CH4 oxidation rate (0.20 mg h−1). The CH4 concentration in the headspace was positively correlated with the AME-AD denitrification rate. The calculated CH4/NO3−(mol/mol) in most treatments ranged from 5.76 to 6.84. In addition, excessively high O2 and CH4 concentrations can lead to increased nitrous oxide (N2O) production in AME-AD. The N2O production rate was up to 1.00 μg h−1 when the O2:CH4 was 1.25:1. These results can provide data support for the application of AME-AD for low-C/N wastewater treatment and greenhouse gas emission reduction.

Wastewater treatment plant effluents increase the global warming potential in a subtropical urbanized river

Rivers play a pivotal role in global carbon (C) and nitrogen (N) biogeochemical cycles. Urbanized rivers are significant hotspots of greenhouse gases (GHGs, N2O, CO2 and CH4) emissions. This study examined the GHGs distributions in the Guanxun River, an effluents-receiving subtropical urbanized river, as well as the key environmental factors and processes affecting the pattern and emission characteristics of GHGs. Dissolved N2O, CO2, and CH4 concentrations reached 228.0 nmol L–1, 0.44 mmol L–1, and 5.2 μmol L–1 during the wet period, and 929.8 nmol L–1, 0.7 mmol L–1, and 4.6 μmol L–1 during the dry period, respectively. Effluents inputs increased C and N loadings, reduced C/N ratios, and promoted further methanogenesis and N2O production dominated by incomplete denitrification after the outfall. Increased urbanization in the far downstream, high hydraulic residence time, low DO and high organic C environment promoted methanogenesis. The strong CH4 oxidation and methanogenic reactions inhibited by the effluents combined to suppress CH4 emissions in downstream near the outfall, and the process also contributed to CO2 production. The carbon fixation downstream from the outfall were inhibited by effluents. Ultimately, it promoted CO2 emissions downstream from the outfall. The continuous C, N, and chlorine inputs maintained the high saturation and production potential of GHGs, and altered microbial community structure and functional genes abundance. Ultimately, the global warming potential downstream increased by 186 % and 84 % during wet and dry periods on the 20-year scale, and increased by 91 % and 49 % during wet and dry periods on the 100-year scale, respectively, compared with upstream from the outfall. In urbanized rivers with sufficient C and N source supply from WWTP effluents, the large effluent equivalently transformed the natural water within the channel into a subsequent "reactor". Furthermore, the IPCC recommended EF5r values appear to underestimate the N2O emission potential of urbanized rivers with high pollution loading that receiving WWTP effluents. The findings of this study might aid the development of effective strategies for mitigating global climate change.

Unveiling the Stability of Encapsulated Pt Catalysts Using Nanocrystals and Atomic Layer Deposition.

Platinum exhibits desirable catalytic properties, but it is scarce and expensive. Optimizing its use in key applications such as emission control catalysis is important to reduce our reliance on such a rare element. Supported Pt nanoparticles (NPs) used in emission control systems deactivate over time because of particle growth in sintering processes. In this work, we shed light on the stability against sintering of Pt NPs supported on and encapsulated in Al2O3 using a combination of nanocrystal catalysts and atomic layer deposition (ALD) techniques. We find that small amounts of alumina overlayers created by ALD on preformed Pt NPs can stabilize supported Pt catalysts, significantly reducing deactivation caused by sintering, as previously observed by others. Combining theoretical and experimental insights, we correlate this behavior to the decreased propensity of oxidized Pt species to undergo Ostwald ripening phenomena because of the physical barrier imposed by the alumina overlayers. Furthermore, we find that highly stable catalysts can present an abundance of under-coordinated Pt sites after restructuring of both Pt particles and alumina overlayers at a high temperature (800 °C) in C3H6 oxidation conditions. The enhanced stability significantly improves the Pt utilization efficiency after accelerated aging treatments, with encapsulated Pt catalysts reaching reaction rates more than two times greater than those of a control supported Pt catalyst.

Synergistic catalysis in Pd/La-CeO2 enhanced CH4 oxidation: The role of water and reactive oxygen species

The catalytic oxidation of methane (CH4) stands as an essential strategy for curtailing greenhouse gas emissions. This study advances CH4 oxidation using Pd on La-doped CeO2, where water (H2O) boosts oxidation efficiency. The temperature for obtaining 50 % CH4 conversion on Pd/La-CeO2 catalyst was reduced from 288 °C (without H2O) to 260 °C (with H2O), while that on CeO2 was 570 °C both under conditions with and without H2O. Operando DRIFTS analysis reveals the reaction pathway and intermediates during CH4 oxidation. Ce cations provide adsorption sites for CH4, leading to the generation of CH3 adsorbed species with the help of surface O2–. La doping creates oxygen vacancies essential for oxygen activation and foster the formation of reactive hydroxide (OH) from adsorbed H2O and O. Pd contributes to the formation of more reactive oxygen species that facilitate OH generation at La cations and the oxidation of CH4 adsorption species to CO2 and H2O. The synergistic interplay between Pd and La-CeO2 is particularly noteworthy, with H2O also playing a role in the gasification of surface carbonates, thereby enhancing the overall performance of CH4 oxidation. A kinetic model based on the Langmuir-Hinshelwood mechanism is proposed, offering an insight into CH4 oxidation.

Microscopic insights into the reaction mechanism of Fe-based oxygen carrier with CH4 in chemical-looping combustion

Fe-based oxygen carriers are regarded as a promising class of oxygen carriers in the field of chemical looping combustion. However, the elucidation of the detailed microscopic reaction mechanism of oxygen carriers remains a significant challenge. In this work, we combine in situ spectroscopy, density-functional theory (DFT) calculations, and micro-kinetic modelling to reveal the microscopic reaction mechanism of CH4 combustion on α-Fe2O3. The macroscopic reaction characterization of hematite with CH4 was carried out on a fixed bed, and gas chromatography (GC) was utilized to detect the combustion products (CO2, H2O and H2). Subsequently, in situ spectroscopy and DFT were combined to reveal the detailed pathways for the CH₄ oxidation process. The results indicated that the reaction intermediates evolve from methoxy (CH3O*) to the bridged bidentate formate (b-HCOO*) to the monodentate formate (m-HCOO*), which ultimately leads to the formation of CO2 through a combination of H transfer and lattice oxygen oxidation. A micro-kinetic model was developed which incorporates surface reaction with the oxygen transport. This revealed that CH3O* and CH3O* → CH2OO* are the key intermediates and radical reactions, respectively, for CO2 production. The elucidation of the reaction mechanism may prove beneficial for the future development of novel Fe-based oxygen carriers.

Efficient oxidation attenuates porewater‐derived methane fluxes in mangrove waters

AbstractMangroves store significant amounts of carbon in both sediment and water. Methane (CH4) is often produced in anoxic, organic‐rich sediments during carbon degradation and released to overlying waters via porewater exchange. Yet, a portion of CH4 can be oxidized to CO2 before emission. Here, we investigate whether CH4 oxidation impacts its emissions using high‐temporal resolution CH4 concentration and stable isotope (δ13C‐CH4) observations collected over 14 tidal cycles in 2 Brazilian mangrove creeks with no river inputs. We found higher CH4 concentrations (~ 150 nM) more depleted in 13C (−75‰) during low tide than high tide at both creeks. Similar δ13C‐CH4 values between low tide surface waters and porewaters further suggest tidally driven porewater exchange as the main source of CH4. More 13C‐enriched CH4 in surface waters and surface sediments than deep sediments indicate partial CH4 oxidation prior to exchange with the atmosphere. A stable isotope mass balance revealed that 17–58% of CH4 was oxidized at rates of 3–25 μmol m−2 d−1 in the water column of tidal creeks. A larger portion of deep porewater CH4 (45–61%) was oxidized in sediments prior to porewater exchange with surface creek waters. The two mangrove creeks had average water–air CH4 fluxes of 51–109 μmol m−2 d−1 over spring‐neap tidal cycles. These aquatic CH4 emissions offset only &lt; 3% of the mangroves' soil carbon sequestration. Overall, CH4 oxidation in both surface water and sediment attenuated CH4 emissions to the atmosphere.

Comparative study on the local hybrid combustion characteristics of the CH4-NH3 laminar premixed flames with/without the wall effects

The CH4-NH3 (50%:50%) premixed flame with/without the wall effects are simulated and compared at the stoichiometric condition in this study. The effects of cold wall and local flame dynamics on the flame temperature, heat release rate (HRR), CH4/NH3 oxidations and local CO/NO formations are analyzed quantitatively. Results show that the flame temperature and HRR are decreased and increased respectively along the flame front towards the axis of free flame, but they are both declined significantly towards the wall owing to suppressed chemical kinetics by the heat loss. The negative flame stretch and differential diffusion at the flame tip suppress the CH4 oxidation and the fast path (NH3→NH2→NH→N2) of NH3 oxidation effectively, but affect the slow path (NH3→NH2→HNO→NO→N2) of NH3 oxidation moderately. This contributes to suppressed CH4/NH3 oxidations and improved NO production at the flame tip of free flame. Based on NRR variations and ROP analysis, compared with CH4 oxidation, wall heat loss exerts stronger suppressions on the fast path of NH3 oxidation, while it decelerates the slow path of NH3 oxidation less evidently. Since the fast path is the primary pathway of the NH3 oxidation, the NH3 oxidation suffers more effective suppression of the wall heat loss than the CH4 oxidation. Furthermore, considering the significance of the slow path to the NO formation, the relatively enhanced importance of the slow path to the NH3 oxidation in the near-wall region predominates the comparatively effective NO formation in the CH4-NH3 flame compared with the pure CH4 flame under the influence of wall heat loss. For the CO/NO formations, the local CO production/oxidation in the wall-impinging CH4-NH3 flame are decelerated simultaneously due to the strong heat loss, while the local NO production/destruction are inhibited/improved by the wall heat loss.

ZIF-8 derived Ag/ZnO photocatalyst with enriched Ag-ZnO interface for effective oxidation of methane to liquid oxygenates with simultaneous mmol-scale productivity and ∼100 % selectivity

Achieving a high yield of oxygenates and inhibiting overoxidation remain challenging for CH4 photooxidation. Here, we report a catalyst with enriched Ag-ZnO interfaces by using ZIF-8 as the precursor. The resulting Ag/Z-450 photocatalysts show extraordinary efficiency in the photocatalytic oxidation of CH4, a high liquid oxygenate yield of 57.88 mmol·gcat−1 (28.94 mmol·gcat−1·h−1) and a selectivity of ∼100 % were obtained over 3.0Ag/Z-450, with HCHO as the major product (41.04 mmol·gcat−1, ∼71 % selectivity). Mechanistic studies revealed that ZnO and Ag species acted as electron donors and acceptors, respectively, which enhanced charge carriers transfer and separation. CH4 and O2 can be effectively activated to generate •CH3 and reactive oxygen species (ROS), their following reaction led to formation of CH3OOH, which can be further converted to CH3OH and HCHO. This work contributes to the development of a “two-in-one” CH4 photooxidation catalyst system that simultaneously achieves unparallel productivity and selectivity.

Environmental determinants of aerobic methane oxidation in a tropical river network

Aerobic methane oxidation (MOX) significantly reduces methane (CH4) emissions from inland water bodies and is, therefore, an important determinant of global CH4 budget. Yet, the magnitude and controls of MOX rates in rivers – a quantitatively significant natural source of atmospheric CH4 – are poorly constrained. Here, we conducted a series of incubation experiments to understand the magnitude and environmental controls of MOX rates in tropical fluvial systems. We observed a large variability in MOX rate (0.03 - 3.45 μmol l-1d-1) shaped by a suit of environmental variables. Accordingly, we developed an empirical model for MOX that incorporate key environmental drivers, including temperature, CH4, total phosphorus, and dissolved oxygen (O2) concentrations, based on the results of our incubation experiments. We show that temperature dependency of MOX (activation energy: 0.66 ± 0.18 eV) is lower than that of sediment methanogenesis (0.71 ± 0.21 eV) in the studied tropical fluvial network. Furthermore, we observed a non-linear relationship between O2 concentration and MOX, with the highest MOX rate occuring ∼135 μmol O2l-1, above or below this “optimal O2” concentration, MOX rate shows a gradual decline. Together, our results suggest that the relatively lower temperature response of MOX compared to methanogenesis along with the projected decrease of O2 concentration due to organic pollution may cause elevated CH4 emission from tropical southeast Asian rivers. Since estimation of CH4 oxidation is often neglected in routine CH4 monitoring programs, the model developed here may help to integrate MOX rate into process-based models for fluvial CH4 budget.

Aerenchyma in emergent plants and rhizospheric microbial communities promote methane fluxes in wetlands

AbstractWetlands are the largest natural source of CH4 globally, yet our understanding of how environmental parameters and microorganisms affect the production and emission of CH4 in emergent plant–sediment systems remains limited. In this study, CH4 fluxes were investigated in a wetland with Canna indica for 42 d, as well as nutrients and microbial community. It was found that the chimney effect formed by aerenchyma in roots, stems, and leaves of C. indica promoted the emission and oxidation of CH4 in the wetland and reduced the CH4 concentration in sediments. Canna indica reduced the nutrient release from surface sediments into the overlying water. Pearson correlation analysis showed that temperature, pH, and oxidation–reduction potential were the main influencing factors for CH4 production and oxidation in the wetland. Canna indica inhibited the diversity of archaeal community but promoted the diversity of bacterial community in the rhizosphere. Stochastic processes had a greater impact on bacterial and archaeal succession trajectories in wetland sediments. Network analysis showed that C. indica promoted interactions among bacteria and archaea that enhanced their ability to resist environmental interference. The well‐developed aerenchyma of C. indica provided an important passage for the transport of CH4 from sediments to the atmosphere and shaped the microbial community structure in the rhizosphere. Meanwhile, CH4 emissions were also constrained by several variables, such as temperature and physiological adaptation in the long term. Thus, it is necessary to plant emergent plants in areas with low CH4 emissions and optimize plant configuration in the context of global warming.

Role of methanogenesis and methanotrophy in CH4 fluxes from rice paddies under elevated CO2 concentration and elevated temperature

The differential responses of methanogenesis and methanotrophy to elevated carbon dioxide concentrations ([CO2]) (e[CO2]) and elevated temperature ([T]) (e[T]) may lead to dramatic changes in the response of CH4 emissions from rice paddies to global warming. In this study, we systematically investigated the responses and mechanisms of CH4 flux from rice paddies to e[CO2] and e[T] based on the production and oxidation of CH4. The CH4 flux, soil properties, and soil methanogenesis and methanotrophy were observed under CK (ambient [CO2] + ambient [T]), EC (e[CO2] by 200 μmol mol−1 + ambient [T]), ET (ambient [CO2] + e[T] by 2 °C), and ECT (e[CO2] by 200 μmol mol−1 + e[T] by 2 °C) treatments. The results revealed that EC, ET, and ECT significantly increased the cumulative amount of CH4 (CAC) in the rice paddies by 10.63, 15.20, and 11.77 kg ha−1, respectively, compared with CK. ECT increased the CAC in the rice paddies by 1.14 kg ha−1 compared with EC. Moreover, EC, ET, and ECT significantly enhanced the methane production potential (MPP) and methane oxidation potential (MOP) and tended to increase the mcrA gene abundance of the methanogens. EC tended to prompt the pmoA gene abundance of the methanotrophs, but the effect of ET on the pmoA gene abundance was less consistent across the growth stages. ECT significantly decreased the relative abundances of Methanosarcina and Methylocystis (Type II) by 4.9 % and 14.2 %, respectively, while it increased the relative abundance of Methylosarcina (Type I) by 24.0 % compared with CK. Overall, the increased MPP/MOP, mcrA/pmoA, and microbial biomass carbon under climate change increased the CH4 flux from the rice paddies. The contribution of e[CO2] to the CH4 flux was significantly enhanced by e[T], which could further exacerbate the risk of global climate change induced by e[CO2].

Tandem Catalysis for Simultaneous Removal of NOx and C3H8 with Inhibition of N2O.

Tandem catalysis is widely adopted for multipollutant control in mobile sources but has rarely been reported in stationary source emission elimination. This work proposed a tandem arrangement way with up-streamed V2O5/TiO2 + down-streamed Cr2O3/TiO2 catalysts, which could achieve the efficient synergistic control of NOx and C3H8 in industrial flue gas. Moreover, this arrangement successfully alleviated the unwanted N2O formation during the NH3 -SCR process. Compared to the conventional impregnation method of the Cr2O3-V2O5/TiO2 catalyst, the tandem catalysts of V2O5/TiO2 + Cr2O3/TiO2 could enhance the NOx and C3H8 conversion by 4.2% and 39.5%, respectively, at 350 °C. It might be attributed to the fact that Cr species was the active site for C3H8 oxidation, and the tandem arrangement of catalysts was beneficial to even dispersion of active components on supports. Furthermore, due to the preferential NOx removal over the up-streamed V2O5/TiO2 catalyst, the tandem catalysts obviously alleviated the N2O formation caused by Cr species during the NH3-SCR process. Herein, it significantly decreased N2O formation by 240.5% at 350 °C compared to the Cr2O3-V2O5/TiO2 catalyst, achieving multipollutant emission control from industrial flue gas with the performance of "one stone three birds".

Electrocatalytic Conversion of CH4 to High Value-Added Liquid Fuel over Binary Metal Oxide Tandem Catalysts

As the main component (> 85%) of combustible ice and shale gas, methane (CH4), plays a significant role in the greenhouse effect.(1) Although CH4 was widely used to synthesize high value-added Cx oxygenates via indirect industrial reforming with high-energy consumption. The accurate control of oxidation degree in CH4 conversion remains a great challenge.(2) Therefore, it is difficult to achieve high conversion rate and high selectivity at the same time. The convenience and reliability of the control of reaction potential, as one of the advantages of electrocatalysis technology, can effectively address the above problems.(1, 3) Electrochemical technologies of CH4-to-Cx oxygenates are regarded as one of the most attractive pathways to produce bulk industrial liquid fuels.(4) Especially in the premise of clean energy as an energy source, the electrochemical conversion of methane demonstrates very advantageous market potential. In this work, we prepared a ZrO2 modified FeOx binary metal oxides tandem catalyst to accelerate partial oxidation of CH4 under ambient condition. With CO3 2- as an oxidant, ZrO2@FeOx tandem catalyst shows remarkable CH4 conversion performance with large current density gap (13.65 mA cm-2) and long-term electrochemical stability (negligible attenuation (8 %) after 48 hours) in three-electrodes cell. In addition, in a flow reactor, ZrO2@FeOx-based electrode also exhibits a highly stable operating lifespan over 72 hours at a large current density 50 mA cm-2 and achieve a feasible CH4-liqid fuel conversion with high total faradaic efficiency.References F. Liu, Y. Yan, G. Chen and D. Wang, Green Chemistry, 26, 655 (2024).S. Yuan, Y. Li, J. Peng, Y. M. Questell-Santiago, K. Akkiraju, L. Giordano, D. J. Zheng, S. Bagi, Y. Román-Leshkov and Y. Shao-Horn, Advanced Energy Materials, 10, 2002154 (2020).M. R. A. Kishore, S. Lee and J. S. Yoo, Adv Sci (Weinh), 10, e2301912 (2023).L. Fu, R. Zhang, J. Yang, J. Shi, H. Y. Jiang and J. Tang, Advanced Energy Materials, 13 (2023).

Oxidative and Reductive Manipulation of C1 Resources by Bio-Inspired Molecular Catalysts to Produce Value-Added Chemicals.

ConspectusTo tackle the energy and environmental concerns the world faces, much attention is given to catalytic reactions converting methane (CH4) and carbon dioxide (CO2) as abundant C1 resources into value-added chemicals with high efficiency and selectivity. In the oxidative conversion of CH4 to methanol, it is necessary to solve the requirement of strong oxidants due to the large bond-dissociation energy (BDE) of the C-H bonds in methane and achieve suppression of overoxidation due to the smaller BDE of the C-H bond in methanol as the product. On the other hand, to efficiently perform CO2 reduction, proton-coupled electron transfer (PCET) processes are required since the reduction potential of CO2 becomes positive by using proton-coupled processes; however, under the acidic conditions required for PCET, hydrogen evolution by the reduction of protons becomes competitive with CO2 reduction. Thus, it is indispensable to develop efficient catalysts for selective CO2 reduction. Recently, we have developed efficient catalytic reactions toward the alleviation of the concerns mentioned above. Concerning CH4 oxidation, inspired by metalloenzymes that oxidize hydrophobic organic substrates, a hydrophobic second coordination sphere (SCS) was introduced to an FeII complex bearing a pentadentate N-heterocyclic carbene ligand, and the FeII complex was used as a catalyst for CH4 oxidation in aqueous media. Consequently, CH4 was efficiently and selectively oxidized to methanol with 83% selectivity and a turnover number of 500. In contrast, when methanol was used as a substrate for catalytic oxidation by the FeII complex, oxidation products were obtained in a negligible yield, which was comparable to that of the control experiment without the catalyst. Therefore, the hydrophobic SCS of the FeII complex can capture only hydrophobic substrates such as CH4 and release hydrophilic products such as methanol to the aqueous medium for suppressing overoxidation ("catch-and-release" mechanism). On the other hand, for photocatalytic CO2 reduction, we have developed NiII complexes with N2S2-chelating ligands as catalysts, which have been inspired by carbon monoxide dehydrogenase, and have also introduced a binding site of Lewis-acidic metal ions to the SCS of the Ni complex. When Mg2+ was applied as a moderate Lewis acid, a Mg2+-bound Ni catalyst allowed us to achieve remarkable enhancement of the photocatalytic CO2 reduction to afford CO as the product with over 99% selectivity and a quantum yield of 11.4%. Divalent metal ions besides Mg2+ also showed similar positive impacts on photocatalytic CO2 reduction, whereas monovalent metal ions exhibited almost no effects and trivalent metal ions exclusively promoted hydrogen evolution. In this Account, we highlight our recent progress in the catalytic manipulations of CH4 and CO2 as C1 resources.

Evaluating the efficacy of biogeochemical cover system in mitigating landfill gas emissions: A large-scale laboratory simulation.

Municipal solid waste (MSW) landfills are a significant source of methane (CH4) emissions in the United States, contributing to global warming. Current landfill gas (LFG) management methods, like the landfill cover system and LFG collection system, do not entirely prevent LFG release. Biocovers have the potential to reduce CH4 emissions through microbial oxidation. However, LFG also contains carbon dioxide (CO2) and trace hydrogen sulfide (H2S) depending on waste composition, temperature, moisture content, and age of waste. An innovative biogeochemical cover (BGCC) was developed to tackle these concerns. This cover comprises a biochar-based biocover layer overlaid with a basic oxygen furnace (BOF) steel slag layer. The biochar-based biocover layer oxidizes CH4 emissions, while the BOF slag layer reduces CO2 and H2S through carbonation and sulfidation reaction mechanisms. The BGCC system's field performance remains unexamined. Therefore, a large-scale tank setup simulating near-field conditions was developed to evaluate the BGCC system's ability to mitigate CH4, CO2, and H2S from LFG simultaneously. Synthetic LFG was passed through the BGCC in five distinct phases, each designed to simulate the varying gas compositions and flux rates typical of MSW landfill. Gas profiles along the depth were monitored during each phase, and gas removal efficiency was measured. After testing, biocover and BOF slag samples were extracted to analyze physico-chemical properties. Batch tests were also conducted on samples extracted from the biocover and BOF slag layers to determine potential CH4 oxidation rates and residual CO2 sequestration capacity. The results showed that the BGCC system's CH4 removal efficiency decreased with higher CH4 flux rates, achieving its highest removal (74.7-79.7%) at moderate influx rates (23.9-25.5g CH4/m2-day) and reducing to its lowest removal (27.4%) at the highest influx rate (57.5g CH4/m2-day). Complete H2S removal occurred during Phase 3 in the biocover layer of BGCC system. CH4 oxidation rates were highest near the upper (277.9µg CH4/g-day) and lowest in the deeper region of the biocover layer. In the tank experiment, CO2 breakthrough occurred after 156days due to drying of the BOF slag layer, with an average residual carbonation capacity of 46 gCO2/kg slag after moisture adjustment. Overall, the BGCC system effectively mitigated LFG emissions, including CH4, CO2, and H2S, at moderate flux rates, showing promise as a comprehensive solution for LFG management.

Enhanced activity and water resistance of SiO2-coated Co/In-SSZ-13 catalysts in the selective catalytic reduction of NOx with CH4

CH4 selective catalytic reduction of NOx (CH4-SCR) is a promising technology to synergistic control of CH4 and NOx emission from LNG-powered vehicles and ships, while its insufficient catalytic activity and H2O resistance are key barriers for application. In this work, SiO2 coated Co3O4/In-SSZ-13 catalysts (Co/In-Z@Si) were prepared to simultaneously improve the CH4-SCR activity and H2O tolerance. The proper Co3O4 introduction enhanced the catalytic performance of the In-SSZ-13, while excessive amount of Co3O4 addition led to more CH4 being oxidized and insufficient CH4 participating in the CH4-SCR reaction. There was a “seesaw effect” between NO oxidation and CH4 oxidation performance of the catalysts. The H2O resistance of the Co/In-Z catalysts significantly enhanced via ultrathin SiO2 coating. The NOx and CH4 conversion maintained 81 % and 90 % in the presence of H2O at 500 °C for the Co/In-Z@Si catalyst, respectively. The in situ DRIFTS confirmed that the SiO2 coating could adsorb H2O molecules, prevent H2O from contacting the active sites, and limit the competitive adsorption between H2O and CH4 on the catalyst. This work provides a good candidate with superior catalytic performance and H2O resistance for removal of NOx and CH4 from LNG-powered vehicles and ships simultaneously.

I2/CAN as an efficient reagent for the direct oxidation of tertiary Csp3-H to Csp3-OH: Synthesis of bis(N-methyl-7-azaindol-3-yl) (phenyl) methanol from 3,3′-(phenyl methylene)-bis(N-methyl-7-azaindole)

I2/CAN has emerged as a powerful and efficient oxidizing agent for direct tertiary CH oxidation of 3,3′-(phenyl methylene) bis(N-methyl-7-azaindole) under mild conditions to form bis(N-methyl-7-azaindol-3-yl) (phenyl)methanol in quantitative yield. Further, based on control experiments, a plausible mechanism and characterization of products including XRD are described. Synthetic transformation for bis(N-methyl-7-azaindol-3-yl) (phenyl) methanol is achieved by thionation.