CH4 Production Research Articles

Dose-dependent effect of spent coffee grounds on intake, apparent digestibility, fermentation pattern, methane emissions, microbial protein supply and antioxidant status in Latxa sheep

Abstract Spent coffee grounds (SCG), a by-product rich in polyphenols, can form part of enteric CH4 mitigation strategies while promoting the circular economy. This study aimed to evaluate the effect of 3 levels of SCG inclusion in the concentrate on enteric CH4 production, feed intake, apparent digestibility, ruminal fermentation pattern, microbial protein supply and gene expression of immune and antioxidant markers in peripheral blood of dry dairy ewes. In a replicated 4 × 4 Latin square design, 8 non-productive Latxa ewes were assigned to a concentrate that differed in the level of SCG: Control (0 g/kg DM), SCG100 (100 g/kg DM), SCG150 (150 g/kg DM) and SCG200 (200 g/kg DM). In each period, 14 days of adaptation were allowed, followed by 7 days in individual metabolic cages, and 3 days in respiratory chambers. To avoid a carry-over effect a minimum of 7 days were allotted between periods in which ewes consumed control concentrate and grass hay. Total organic matter intake (OMI) and CH4 emissions (g/d) presented a quadratic response (P=0.008 and P<0.001, respectively) to increasing levels of SCG in the feed. However, when CH4 emissions were corrected for OMI, a linear decrease was observed with increasing levels of SCG in the concentrate (P=0.009). This reduction in CH4 emissions (g/kg OMI) could be explained by the linear decrease (P=0.034) observed in apparent digestibility of organic matter (OM), particularly in crude protein (CP) and starch (P=0.002 and P=0.003, respectively), with increasing levels of SCG in the concentrate. No significant response was found on CH4 emissions corrected for digestible OM and on ruminal fermentation pattern. Regarding microbial protein supply, a linear increase in microbial protein supply efficiency (P=0.008) was observed with increasing levels of SCG in the concentrate. Moreover, SCG inclusion linearly reduced interleukin 10 (P=0.031), nuclear factor E2-related factor 2 (P=0.007), nuclear factor kappa β (P=0.014), superoxide dismutase 1 (P=0.015) gene expression and tended to linearly reduce those of tumor necrosis factor-α (P=0.074) and glutathione peroxidase 1 (P=0.082). In conclusion, inclusion of SCG up to 200 g/kg in the concentrate did not modify ruminal fermentation pattern, but linearly reduced CH4 emissions per kg of OMI, due to a linear decrease in apparent digestibility of CP and starch. Moreover, linearly increased the efficiency of microbial supply and improved sheep’s blood antioxidant-immune status.

High‐Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates‐Stabilized *CO Intermediate

AbstractStabilizing specific intermediates to produce CH4 remains a main challenge in solar‐driven CO2 reduction. Herein, g‐C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x=12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80 % and 40.8 μmol ⋅ g−1 ⋅ h−1 evolution rate for PW9/g‐C3N4. Conversely, g‐C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g‐C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g‐C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g‐C3N4 (x=12, 11) compared with that of PW9/g‐C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.

Dual‐Site NiO/Bi3O4Br Heterojunction Catalyst for High‐Efficiency CO2‐to‐CH4 Conversion

Solar light‐driven conversion of CO2 into chemicals with high calorific value is regarded as an up‐and‐coming carbon utilization technology for alleviating the energy crisis. This technique faces the challenge of low CO2 conversion and product yield due to charge recombination in the catalyst. In this paper, a dual‐reaction‐site heterojunction catalyst was designed and fabricated by combining NiO with Bi3O4Br nanosheets, for the separation of CO2 reduction and H2O oxidation semireactions, which effectively promoted electrons and holes separation. The resulting catalyst exhibited a high CH4 production rate (8.12 μmol/g) and selectivity (94.69%). Electron distribution and band structure were investigated to explain the satisfactory catalytic performance. In addition, combining the in‐situ DRIFTS results, a formic acid‐intermediated CO2‐to‐CH4 reaction pathway was proposed. This work aims to pave the way for CH4 production via CO2 photoreduction with high efficiency and selectivity.

The Hydration-Dependent Dynamics of Greenhouse Gas Fluxes of Epiphytic Lichens in the Permafrost-Affected Region

Recent studies actively debate oxic methane (CH4) production processes in water and terrestrial ecosystems. This previously unknown source of CH4 on a regional and global scale has the potential to alter our understanding of climate-driving processes in vulnerable ecosystems, particularly high-latitude ecosystems. Thus, the main objective of this study is to use the incubation approach to explore possible greenhouse gas (GHG) fluxes by the most widely distributed species of epiphytic lichens (ELs; Evernia mesomorpha Nyl. and Bryoria simplicior (Vain.) Brodo et D. Hawksw.) in the permafrost zone of Central Siberia. We observed CH4 production by hydrated (50%–400% of thallus water content) ELs during 2 h incubation under illumination. Moreover, in agreement with other studies, we found evidence that oxic CH4 production by Els is linked to the CO2 photoassimilation process, and the EL thallus water content regulates that relationship. Although the GHG fluxes presented here were obtained under a controlled environment and are probably not representative of actual emissions in the field, more research is needed to fully comprehend ELs’ function in the C cycle. This particular research provides a solid foundation for future studies into the role of ELs in the C cycle of permafrost forest ecosystems under ongoing climate change (as non-methanogenesis processes in oxic environments).

CO2-free production of hydrogen via pyrolysis of natural gas: influence of non-methane hydrocarbons on product composition, methane conversion, hydrogen yield, and carbon capture

Methane pyrolysis represents a CO2-free hydrogen production route that enables simultaneous carbon capture. While the majority of previous studies in the field focus on pure CH4 as feed gas stream, commercial processes will typically rely on natural gas as feedstock that contains also non-methane hydrocarbons such as ethane, propane, and n-butane. Therefore, the present study evaluates how CH4 conversion, H2 selectivity, product composition, and solid carbon yield evolve when using either pure CH4 or synthetic natural gas (SNG) as feed gas stream for a thermal pyrolysis process in a lab-scale high-temperature reactor. For this, industrially viable conditions are applied, namely temperatures between 1000 °C and 1600 °C, residence times between 1 s and 7 s, and molar H2 dilution ratios between 1:1 and 4:1. Although the use of SNG results in slightly lower hydrocarbon conversions because the additional components in SNG result in a higher effective H2 dilution ratio compared to a CH4-only feed, the non-methane hydrocarbons in the SNG have a positive effect on both H2 selectivity and solid carbon yield. Taking existing mechanistic understanding into account, these positive effects are attributed to radicals formed from the non-methane hydrocarbons, which facilitate dehydrogenation steps from ethane to ethylene and hereby increase the relative amount of H2 originating from CH4. The introduction of a carbonaceous fixed bed further benefits the performance of the pyrolysis process and ultimately enables to capture more than 98% of carbon in its solid form under industrially viable process conditions.

Integrated Carbon Dioxide Capture by Amines and Conversion to Methane on Single-Atom Nickel Catalysts.

Direct electrochemical reduction of carbon dioxide (CO2) capture species, i.e., carbamate and (bi)carbonate, can be promising for CO2 capture and conversion from point-source, where the energetically demanding stripping step is bypassed. Here, we describe a class of atomically dispersed nickel (Ni) catalysts electrodeposited on various electrode surfaces that are shown to directly convert captured CO2 to methane (CH4). A detailed study employing X-ray photoelectron spectroscopy (XPS) and electron microscopy (EM) indicate that highly dispersed Ni atoms are uniquely active for converting capture species to CH4, and the activity of single-atom Ni is confirmed using control experiments with a molecularly defined Ni phthalocyanine catalyst supported on carbon nanotubes. Comparing the kinetics of various capture solutions obtained from hydroxide, ammonia, primary, secondary, and tertiary amines provide evidence that carbamate, rather than (bi)carbonate and/or dissolved CO2, is primarily responsible for CH4 production. This conclusion is supported by 13C nuclear magnetic resonance (NMR) spectroscopy of capture solutions as well as control experiments comparing reaction selectivity with and without CO2 purging. These findings are understood with the help of density functional theory (DFT) calculations showing that single-atom nickel (Ni) dispersed on gold (Au) is active for the direct reduction of carbamate, producing CH4 as the primary product. This is the first example of direct electrochemical conversion of carbamate to CH4, and the mechanism of this process provides new insight on the potential for integrated capture and conversion of CO2 directly to hydrocarbons.

The green footprint of anammox processes under simulated actual operating conditions: Focusing on the nitrous oxide and methane production

The anammox process has attracted increasing attention due to its advantages of low-carbon and energy-saving, nevertheless, greenhouse gas was still generated during its engineering applications process. Hence, it is vital to comprehensively understand the production characteristics and mechanisms of N2O and CH4 in anammox processes by responding to practical conditions including dissolved oxygen, temperature, and salinity. Results showed that N2O production increased by 192 %–358 %, while nitrogen removal efficiency (NRE) increased by 64.2 %–86.8 % with increasing temperature. The increased salinity inhibits 40.60 %–65.33 % N2O production with a decrease NRE of 7.85 %–18.2 %. CH4 production was the highest at 18–27 °C, reaching 3.07 ± 0.11–4.06 ± 0.16 mg·L−1, which were 1.59–2 and 1.29–1.38 times higher than that at 8–17 °C and 28–37 °C, respectively. Denitratisoma, Thauera, and Nitrosomonas were the main functional microbes for greenhouse gas production in anammox consortia. Notably, H2O2-induced intracellular Fenton reaction may be critical for the CH4 production in anammox consortia. This work provides valuable insights into achieving efficient nitrogen removal and minimizing carbon footprint in anammox systems and provides a theoretical basis for implementing the net-zero emission idea in wastewater treatment plants.

Optimized Carbon Coupling for Enhanced Ethylene Production via a Unique Single-Atom-Substrate Synergy Mechanism within Photocatalytic Processes.

The utilization of solar-driven technologies for the direct conversion of methanol (CH3OH) into two or multi-carbon compounds through controlled carbon-carbon (C-C) coupling is an appealing yet challenging objective. In this study, we successfully demonstrate the photocatalytic CH3OH coupling to ethylene (C2H4), a valuable chemical raw material, by employing a carbon nitride-based catalyst. Specifically, we modify the layered polymer carbon nitride (PCN) photocatalyst through the incorporation of Au single atoms (Au1/PCN) using a chemical-scissors method. The synergistic effect between the PCN substrate and the Au single atoms reduces the potential barrier associated with C-C coupling, thereby enhancing the efficiency of CH3OH reforming to C2H4. This investigation not only reveals a novel pathway for C2H4 production via CH3OH reforming but also provides fresh insights into the possibilities of C-C coupling.

Opportunities for biogas production from algal biomass

Energy security is a critical global challenge in the transition to sustainable development. Anaerobic digestion (AD) offers a promising renewable energy solution that mitigates environmental impacts. Algae, as biomass feedstock, have shown significant potential for bioenergy production; however, their complex chemical composition poses challenges to the efficiency of the AD process. To address these limitations, various pretreatment methods have been applied to enhance biogas production. In this study, we performed a comprehensive meta‐analysis to evaluate the effects of different pretreatments on methane (CH₄) yields from both microalgae and macroalgae. Our results demonstrate that biological, physical, and combined chemical–physical pretreatments significantly improve CH₄ production in microalgae, with increases of up to 141%, 125%, and 151%, respectively. For macroalgae, physical pretreatments were the most effective, leading to a 129% increase in CH₄ yield. We also estimate that utilizing just 10% of the global algal biomass production (3.6 Mt) could generate over 5.5 TWh y−1 of energy. This potential could be doubled with the application of appropriate pretreatment strategies. These findings highlight the role of algae in advancing renewable energy production and contribute to the growing body of knowledge on optimizing AD processes for cleaner energy generation.

Higher temperatures exacerbate effects of antibiotics on methanogenesis in freshwater sediment

Methane (CH4) emissions from natural systems are rising in a concerning manner with an incomplete understanding of its drivers. Recently, chemical stressors such as antibiotics have been suggested as a thus far overlooked factor increasing methanogenesis in freshwaters. Since usage and toxicological impact of antibiotics could increase in a warming climate, we assessed the temperature-dependence of antibiotic effects on methanogenesis. In this light, we conducted anaerobic incubations with freshwater sediment at 10, 15, and 20 °C in presence of a mixture of five antibiotics at field-relevant concentrations. Weekly measurements of CH4 showed a strong temperature dependence of antibiotic effects by changing effect sizes, directions and dynamics. While antibiotics reduced CH4 production at 10 °C, methanogenesis was elevated at 15 °C with the most pronounced increase occurring at 20 °C. Furthermore, antibiotics changed the prokaryotic assemblage at all temperatures and effect patterns of CH4 producing Methanomicrobia strongly followed the patterns observed for methanogenesis. While analyses of compound-specific stable isotopes and the metatranscriptome suggest the acetoclastic pathway as most relevant, linking prokaryotic structure to function remains one of the most significant research challenges. Nevertheless, the evidence provided by this study suggests a positive relationship between temperature and the stimulating effects of antibiotics on CH4 production.

Effects of inorganic nitrogen enrichment on soil CH4 and CO2 production in freshwater and mesohaline marshes across six estuaries in China

Eutrophication is an important environmental stressor in coastal wetlands that alters ecosystem processes including primary production and the carbon cycle. However, how different nitrogen eutrophication scenarios may affect CH4 and CO2 production along a salinity gradient in coastal wetlands is poorly known. We collected the surface soil samples from both tidal freshwater and mesohaline Phragmites australis marshes in six main estuaries in China and conducted inorganic nitrogen enrichment anaerobic incubation experiments. Background soil CH4 and CO2 production rates were strongly correlated with total nitrogen but not salinity. On average, nitrate enrichment decreased soil CH4 and CO2 production rates by ca. 20 % in freshwater marsh and 16–43 % in mesohaline marshes, whereas ammonium enrichment decreased CO2 production by ca. 26–30 % but had no effect on CH4 production. Salinity was not an important mitigating factor in either eutrophication scenario. In most cases, nitrogen addition decreased the extracellular enzyme activities of β-1,4-glucosidase and cellobiohydrolase, but increased the activity of β-N-acetyl glucosaminidase, phenol oxidase and peroxidase. Nitrate addition decreased the mcrA gene abundance on average by 34–35 % but ammonium addition had insignificant effect. Total nitrogen availability was an important driver of CH4 and CO2 production rates in these tidally influenced coastal wetlands. Our results showed that tidal marshes with salinity < 15 ppt had similar soil CH4 production rates, and increasing inorganic nitrogen eutrophication might lower soil microbial carbon gas production in both tidal freshwater and mesohaline marshes.

Utilization of dissolved CO2 to control methane and acetate production in methanation reactor

This study investigated the influence of dissolved CO2 on the selection of metabolic pathway using a methanation membrane bioreactor supplied with H2/CO2. Various ratios of H2/CO2 were applied (3.3, 3.8, 4.0, 4.5, and 5.0 (v/v)) to manipulate dissolved CO2 levels in the medium. The findings revealed a correlation between the concentration of dissolved CO2 and the production of CH4 (positive) and acetate (negative). Specifically, at a dissolved concentration of CO2 above 2.0 ± 0.2 mmol/L, production of CH4 was favored. At the opposite, acetate production was favored at lower dissolved CO2 concentrations, with a maximum concentration of 1.9 g/L observed at 0.9 mmol/L of dissolved CO2. This study demonstrates that the modification of dissolved CO2 levels in a methanation bioreactor can provide a strategy for the selection of metabolic pathways and microbial communities, thereby offering a promising opportunity for optimizing the conversion of CO2 into high-value products such as CH4 and acetate.

Modulating the chemical environment of Ni2+ for the oxidative dehydrogenation of ethane: The formation of LAS(Al3+/Ga3+)-Ni-OH site

The oxidative dehydrogenation of ethane to ethylene (ODHE) usually suffers from the issues of ethane conversion-ethylene selectivity seesaw. Herein, a series of alumina-supported Ni and Ga catalysts with different molar ratios of Ni to Ga were synthesized by facile impregnation method constructing the Lewis acid site (LAS) strategy to obtain great ethylene selectivity (97 %). The variation of Ni:Ga ratio adjusted the ionic substitution ability, redox ability and acidity, thus regulate the chemical environment of Ni2+ to the formation of LAS(Al3+/Ga3+)-Ni-OH structure, which was proposed to be the active site for selective oxidation of ethane to ethylene, as proved by H2-TPR, ToF-SIMS, quasi in-situ XPS and in-situ FTIR. Moreover, the probable mechanism of ODHE reaction was proposed that C2H6 molecules were mainly adsorbed on LAS sites and activated on Ni-OH site of the catalyst. The pulse test further suggested that O- was mainly associated with the generation of CO2 and Ni(2-n)+ was connected with the production of CH4. It is highlighted that adjusting the Ni-related species and oxygen species on the catalyst surface are crucial to further improve the ethylene selectivity.

Enhancing effect of conductive materials and rumen microorganisms on the anaerobic digestion performance of a real traditional Chinese medicine wastewater

This work evaluated the effect of different concentrations of conductive materials and rumen microorganisms on the anaerobic digestion (AD) performance of real traditional Chinese medicine (TCM) wastewater. The experiments first determined the optimal organic concentration of 0.25 L/L for the AD system and removed suspended solids from real TCM wastewater to reduce the inhibition effect on methanogenesis. Analysis of the modified Gompertz model showed that the addition of activated carbon, biochar, cow manure, and rumen fluid at doses of 12 g/L, 12 g/L, 12 mL/L, and 125 mL/L, respectively, had the greatest effect on CH4 production, increasing the cumulative CH4 yield by 13.5 %, 10.4 %, 26.8 %, and 32.9 %. Through microbial community and metabolism pathway analyses, the conductive materials promoted direct interspecies electron transfer (DIET) between Clostridium and Methanothrix, and the acetoclastic methanogenic pathway dominated by acetyl-CoA synthase. Rumen microorganisms enhanced AD performance by promoting the growth of hydrogenotrophic methanogens and the abundance of genes dominated by formylmethanofuran dehydrogenase in the hydrogenotrophic methanogenic pathway, illustrating the relationship between microbial community and metabolism pathway. Rumen microorganisms increased CH4 production more than conductive materials in real TCM wastewater. This study helps to better understand the internal mechanisms by which different materials enhance AD performance.

Sulfate availability affect sulfate reduction pathways and methane consumption in freshwater wetland sediments

Methane (CH4) emissions from wetlands significantly contribute to global greenhouse gas fluxes, yet the mechanisms regulating CH4 production and oxidation in freshwater wetlands remain underexplored, particularly in the role of sulfate in the anaerobic oxidation of CH4. This study investigated the production, consumption, and release of CH4 in the sediments of the Qilihai wetland, focusing on the roles of hydrogenotrophic methanogenesis and sulfate dynamics across different seasons. CH4 concentrations ranged from 2.42 to 2290.52 μmol L⁻1, and δ13C–CH4 values became progressively more negative with depth, ranging from −87.37‰ to −57.18‰. Results indicate that hydrogenotrophic methanogenesis is the dominant pathway for CH4 production, particularly in sulfate-depleted environments, with CH4 concentrations in the sulfate-methane transition zone (SMTZ) strongly correlated with sulfate availability. Sulfate consumption through Sulfate Anaerobic Oxidation of Methane (SAOM) and Organoclastic Sulfate Reduction (OSR) demonstrated significant seasonal variation, with OSR accounting for up to 73% of sulfate consumption in the SMTZ. The SMTZ exhibited variations ranging from 2 to 40 cm in October, narrowing to 2–4 cm in July. These findings emphasize the complex interactions between sulfate availability, methanogenic pathways, and CH4 emissions in freshwater wetlands, highlighting the need for further research on sulfate dynamics and their implications for greenhouse gas emissions in the context of global climate change.

Mixed atomic-scale electronic configuration as a strategy to avoid cocatalyst utilization in photocatalysis

To enhance the activity of photocatalysts for hydrogen production and CO2 conversion, noble metal cocatalysts as electron traps and/or acceptors such as platinum or gold are usually utilized. This study hypothesizes that mixing elements with heterogeneous electronic configurations and diverse electronegativities can provide both acceptor and donor sites of electrons to avoid using cocatalysts. This hypothesis was examined in high-entropy oxides (HEOs), which show high flexibility for atomic-scale compositional changes by keeping their single- or dual-phase structure. A new high-entropy oxide was designed and synthesized by mixing elements with an empty d orbital (titanium, zirconium, niobium and tantalum) and a fully occupied d orbital (gallium). The synthesized oxide had two phases (88 wt% orthorhombic (Pbcn) and 12 wt% monoclinic (I2/m)) with an overall composition of TiZrNbTaGaO10.5. It exhibited UV and visible light absorbance with a low bandgap of 2.5 eV, low radiative electron-hole recombination and oxygen vacancy generation due to mixed valences of cations. It successfully acted as a photocatalyst for CO and CH4 production from CO2 conversion and hydrogen production from water splitting without cocatalyst addition. These findings confirm that introducing heterogeneous electronic configurations and electronegativities can be considered as a design criterion to avoid the need to use cocatalysts.

Diel Greenhouse Gas Emissions Demonstrate a Strong Response to Vegetation Patch Types in a Freshwater Wetland

AbstractWetland methane (CH4) fluxes are highly variable over spatial and temporal scales due to variations in CH4 production, oxidation, and transport. While some aspects of temporal variability in CH4 fluxes are well documented, diel variability is poorly constrained, and studies report conflicting findings, making it difficult to generalize. Topographic, geochemical, hydroclimatic, and vegetative variability can result in characteristically different “patches” that likely influence differences in diel patterns. We investigated diel patterns of CH4 fluxes from a large seasonal‐mineral soil wetland in Maryland (USA) across three functionally unique patches: two with vegetation (emergent and submerged aquatic vegetation) and one without (open water) during the summer of 2021. To explore the relationships between vegetation, environmental conditions, and flux patterns, we also measured physiochemical variables (air and water temperature, pH, relative humidity, PAR, dissolved oxygen, and water depth). To our knowledge, this is the first study comparing diel variability using chambers across such distinct vegetation patch types. We found that diel patterns were strongly linked to patch types: CH4 fluxes from the emergent vegetation did not display a consistent diel pattern, while fluxes from the submerged vegetation and no vegetation patches frequently peaked at 13:00 and 05:00, respectively. These differences could be a direct result of vegetation impact on production, oxidation, and/or transport of CH4 or on conditions covarying with patch type. This study contributes to the growing understanding of how CH4 fluxes vary spatially over diel cycles and emphasizes the importance of considering spatially varying diel patterns when estimating fluxes.

Oxygen vacancies–elusive but common catalytic key defects for thermal upgrading of CO2 to CH4, CO and CH3OH

Single carbon products (C1 compounds) are simple but important chemicals in the road towards energy transition. Catalytic conversion of CO2 with H2 (desirably renewable) can be performed over reducible oxides supporting transition metals to obtain products such as CH4, CO and MeOH. Oxygen vacancies (O-vacancies), which are inherent defects of reducible metal oxides, play an enormous role in driving the catalytic performance (activity, selectivity, stability) for the desired reactions. Yet, the assessment of O-defects at realistic conditions is often complex. Only few techniques can provide direct evidence for their existence and influence in CO2 activation. Among them, electron paramagnetic spectroscopy (EPR), Raman spectroscopy, scanning probe microscopies (SPM) and environmental transmission electron microscopy (ETEM) are nowadays the most informative. In most cases, however, the measurements require reaction conditions far away from CO2 valorization applications. Although great efforts have been fruitful in explaining and demonstrating the huge importance of O-vacancies in CO2 catalysis, still ambiguous or erroneous interpretations about structure-function correlations involving O-vacancies are found in literature, especially, when information is not properly gathered, e.g., by O 1s ex-situ X-ray photon spectroscopy (XPS). Moreover, despite the recognized importance of O-vacancies for CO2 valorization, critical literature compilations about their effects in thermal processes are scarce. Herein, we attempt to contribute in closing this gap by integrally encompassing representative investigations on the thermo-catalytic production of CH4, CO and MeOH. Particularly, we emphasize in the proper selection of assessment tools (direct/indirect) to unambiguously establish structure-function relationships to design optimized O-defective catalysts for the targeted compounds.

New approach to agro-industrial solid and liquid waste management: Performance of an EGSB reactor at different hydraulic retention times for methane production

This study investigated the removal of agro-industrial wastes (5 g COD L⁻1 from coffee and 0.5 g COD L⁻1 from brewery wastewater, plus 1 g L⁻1 of coffee pulp and husk) in a continuous Expanded Granular Sludge Bed (EGSB) reactor at 35 °C. The effect of Hydraulic Retention Times (HRTs) of 72h, 48h, and 24h on CH₄ yield was examined using a mixed culture of cattle manure and granular sludge. Methane yields were 201, 124.5, and 113.8 mL CH₄ g⁻1 COD for the 1st, 2nd, and 3rd phases, respectively. Volatile fatty acids, particularly acetic acid, increased at lower HRTs. Sequencing of the 16S rRNA gene on the Illumina HiSeq platform revealed a syntrophic relationship between Syntrophorhabdus, Syntrophobacter, and Pseudomonas with methanogens Methanomassiliicoccus, Methanospirillum, and Methanobacterium, aiding in the removal of phenolic compounds. The study suggests that an HRT of 72h is optimal for maximizing CH₄ production in the EGSB reactor.

Very low Ru loadings boosting performance of Ni-based dual-function materials during the integrated CO2 capture and methanation process

Herein, the effect of the Ru:Ni bimetallic composition in dual-function materials (DFMs) for the integrated CO2 capture and methanation process (ICCU-Methanation) is systematically evaluated and combined with a thorough material characterization, as well as a mechanistic (in-situ diffuse reflectance infrared fourier-transform spectroscopy (in-situ DRIFTS)) and computational (computational fluid dynamics (CFD) modelling) investigation, in order to improve the performance of Ni-based DFMs. The bimetallic DFMs are comprised of a main Ni active metallic phase (20 wt%) and are modified with low Ru loadings in the 0.1–1 wt% range (to keep the material cost low), supported on Na2O/Al2O3. It is shown that the addition of even a very low Ru loading (0.1–0.2 wt%) can drastically improve the material reducibility, exposing a significantly higher amount of surface-active metallic sites, with Ru being highly dispersed over the support and the Ni phase, while also forming some small Ru particles. This manifests in a significant enhancement in the CH4 yield and the CH4 production kinetics during ICCU–Methanation (which mainly proceeds via formate intermediates), with 0.2 wt% Ru addition leading to the best results. This bimetallic DFM also shows high stability and a relatively good performance under an oxidizing CO2 capture atmosphere. The formation rate of CH4 during hydrogenation is then further validated via CFD modelling and the developed model is subsequently applied in the prediction of the effect of other parameters, including the H2 inlet concentration, inlet flow rate, dual-function material weight, and reactor internal diameter.