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Effective conversion of methane to a mixture of more valuable hydrocarbons and hydrogen under mild conditions is a great scientific and practical challenge. Here, we synthesized Zn-containing nanosized MFI zeolite for direct oxidation of methane in the presence of H2O and air. The presence of the surface hydroxyl groups on nanosized MFI-type zeolite and their significant reduction in the Zn-containing nanosized MFI zeolite were confirmed with Infrared Fourier Transform (FTIR) spectroscopy. Incorporation of zinc atoms into the framework of nanosized MFI zeolite is revealed by Nuclear Magnetic Resonance, X-ray Diffraction a UV-Vis Spectroscopy. Unexpectedly, pure silica MFI zeolite exhibited the highest photocatalytic performance. Our finds demonstrated that large number of isolated silanol groups and silanol nests increase the formation of •OH, and enhance the productivity of oxygenate compounds and C2H6, while the Zn incorporated into the zeolite framework or attached to the silanol nests of the nanosized zeolites are less efficient. A mechanism of photocatalytic methane oxidation is proposed. These findings provide insights into developing active nanosized zeolite photocatalysts with extended amount of surface hydroxyl groups that can play a key role in photocatalytic methane conversion.

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The acidic electrocatalytic conversion of CO2 to multi-carbon (C2+) oxygenates is of great importance in view of enhancing carbon utilization efficiency and generating products with high energy densities, but suffering from low selectivity and activity. Herein, we synthesized Ag-Cu alloy catalyst with highly rough surface, by which the selectivity to C2+ oxygenates can be greatly improved. In a strongly acidic condition (pH=0.75), the maximum C2+ products Faradaic efficiency (FE) and C2+ oxygenates FE reach 80.4% and 56.5% at -1.9 V versus reversible hydrogen electrode, respectively, with a ratio of FEC2+ oxygenates to FEethylene up to 2.36. At this condition, the C2+ oxygenates partial current density is as high as 480 mA cm-2. The in situ Raman measurements and control experiments indicate that the high generation of C2+ oxygenates over the catalyst originates from its large surface roughness and Ag alloying.

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High-entropy compounds have been emerging as promising candidates for electrolysis, yet their controllable electrosynthesis strategy remains a formidable challenge because of the ambiguous ionic interaction and codeposition mechanism. Herein, we report a oxygenates directionally induced electrodeposition strategy to construct high-entropy materials with amorphous features, on which the structural evolution from high-entropy phosphide to oxide is confirmed by introducing vanadate, thus realizing the simultaneous optimization of composition and structure. The representative P-CoNiMnWVOx shows excellent bifunctional catalytic performance toward alkaline hydrogen evolution reaction and ethanol oxidation reaction (EOR), with small potentials of -168 mV and 1.38 V at 100 mA cm-2, respectively. In situ spectroscopy illustrates that the electrochemical reconstruction of P-CoNiMnWVOx induces abundant Co-O species as the main catalytic active species for EOR and follows the conversion pathway of the C2 product. Theoretical calculations reveal the optimized electronic structure and adsorption free energy of reaction intermediates on P-CoNiMnWVOx, thereby resulting in a facilitated kinetic process. A membrane-free electrolyzer delivers both high Faradaic efficiencies of acetate and H2 over 95% and superior stability at100 mA cm-2 during 120 h electrolysis. In addition, the unique composition and structural advantages endow P-CoNiMnWVOx with multifunctional catalytic activity and realize multipathway electrosynthesis of formate-coupled hydrogen production.

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Substantial amounts of low-value light petroleum fractions and low-value heavy petroleum fractions, such as light naphtha, HVGO, and vacuum residue, are generated during the upgrading and refining of conventional and unconventional petroleum resources. The oil industry emphasizes economic diversification, aiming to produce high-value products from these low petroleum fractions through cost-effective and sustainable methods. Controlled autoxidation (oxidation with air) has the potential to produce industrially important oxygenates, including alcohols, and ketones, from the low-value light petroleum fractions. The produced alcohols can also be converted to olefin through catalytic dehydration. Following controlled autoxidation, the low-value heavy petroleum fractions can be utilized to produce value-added products, including carbon fiber precursors. It would reduce the production cost of a highly demandable product, carbon fiber. This review highlights the prospect of developing an alternative, sustainable, and economic method to produce value-added products from the low-value petroleum fractions following a controlled autoxidation approach.

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Maintaining high conversion under the premise of high oxygenates selectivity in syngas conversion is important but a formidable challenge in Rh catalysis. Monometallic Rh catalysts provide poor oxygenate conversion efficiency, and efforts have been focused on constructing adjacent polymetallic sites; however, the one-pass yields of C2+ oxygenates over the reported Rh-based catalysts were mostly <20 %. In this study, we constructed a monometallic Rh catalyst encapsulated in UiO-67 (Rh/UiO-67) with enhanced proximity to dual-site Rh1,2-Rhn ensembles. Unexpectedly, this catalyst exhibited high efficacy for oxygenate synthesis from syngas, giving a high oxygenate selectivity of 72.0 % with a remarkable CO conversion of 50.4 %, and the one-pass yield of C2+ oxygenates exceeded 25 %. The state-of-the-art characterizations further revealed the spontaneous formation of an ensemble of Rh single atoms/dimers (Rh1,2) in the proximity of ultrasmall Rh clusters (Rhn) confined within the nanocavity of UiO-67, providing adjacent Rh+-Rh0 dual sites dynamically during the reaction that promote the relay of the undissociated CHO species to the CHx species. Thus, our results open a new route for designing highly efficient Rh catalysts for the conversion of syngas to oxygenates by precisely tuning the ensemble and proximity of the dual active sites in a confined space.

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Direct photocatalytic methane oxidation into value-added products provides a promising strategy for methane utilization. However, the inefficient generation of reactive oxygen species (ROS) partly limits the activation of CH4. Herein, it is reported that Pd and VOδ co-modified TiO2 enables direct and selective methane oxidation into liquid oxygenates in the presence of O2 and H2. Due to the extra ROS production from the in situ formed H2O2, a highly improved yield rate of 5014 µmol g-1 h-1 for liquid oxygenates with a selectivity of 89.3% is achieved over the optimized Pd0.5V0.2-TiO2 catalyst at ambient temperature, which is much better than those (2682 µmol g-1 h-1, 77.8%) without H2. Detailed investigations also demonstrate the synergistic effect between Pd and VOδ species for enhancing the charge carrier separation and transfer, as well as improving the catalytic activity for O2 reduction and H2O2 production.

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Understanding anaerobic biodegradation of ether oxygenates beyond MTBE in groundwater is important, given that it is replaced by ETBE as a gasoline additive in several regions. The lack of studies demonstrating anaerobic biodegradation of ETBE, and its product TBA, reflects the relative resistance of ethers and alcohols with a tertiary carbon atom to enzymatic attack under anoxic conditions. Anaerobic ETBE- or TBA-degrading microorganisms have not been characterized. Only one field study suggested anaerobic ETBE biodegradation. Anaerobic (co)metabolism of ETBE or TBA was reported in anoxic microcosms, indicating their biodegradation potential in anoxic groundwater systems. Non-isotopic methods, such as the detection of contaminant loss, metabolites, or ETBE- and TBA-degrading bacteria are not sufficiently sensitive to track anaerobic biodegradation in situ. Compound- and position-specific stable isotope analysis provides a means to study MTBE biodegradation, but isotopic fractionation of ETBE has only been studied with a few aerobic bacteria (εC -0.7 to -1.7‰, εH -11 to -73‰) and at one anoxic field site (δ2H-ETBE +14‰). Similarly, stable carbon isotope enrichment (δ13C-TBA +6.5‰) indicated TBA biodegradation at an anoxic field site. CSIA and PSIA are promising methods to detect anaerobic ETBE and TBA biodegradation but need to be investigated further to assess their full potential at field scale.

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The study was performed in two phases. First, the polymerization was carried out upon three magnetized surfaces of silica aerogel, zeolite Y, and MIL-101(Cr). Then, optimal molecularly imprinted polymer and optimal extraction conditions were determined by the central composite design-response surface method. Subsequently, the validation parameters of dispersive solid-phase extraction based optimal molecularly imprinted polymer were examined for the extraction of the fuel ether oxygenates. The optimal conditions include the type of adsorbent: Zeolite-magnetic molecularly imprinted polymer, the amount of adsorbent: 40 mg, pH: 7.7, and absorption time: 24.8 min which was selected with desirability equal to 0.996. The calibration graphs were linear between 1 and 100 µg L-1, with good correlation coefficients. The limits of detection were found to be 0.64, 0. 4, and 0.34 µg L-1 for methyl tert-butyl ether, ethyl tert-butyl ether, and tert butyl formate, respectively. The method proved reliable for analyzing fuel ether oxygenates in drinking water.

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Accurate estimation of oxygenates is a critical issue in the quality evaluation of gasoline samples. This work aims to examine the nonparametric robust principal component analysis-alternating conditional expectation (rPCA-ACE) algorithm combined with FTIR spectroscopy as a rapid and accurate analytical method for predicting the quality of gasoline samples based on oxygenates content (methanol, methyl tert-butyl ether, and isobutanol). In the ACE algorithm, a set of optimal transformations is estimated for both the independent and dependent variables. These transformations reveal their non-linear relationships and generate a maximum linear effect between the transformed independent variables and the transformed response variable. In this study, the ACE algorithm was applied to an empirical gasoline dataset and considered a series of possible transformations of the independent and dependent variables to find the best transformations. Among all possible transformations, the ACE algorithm identified a series of polynomials and a nearly linear transformation as the best transformations for the independent and dependent variables, respectively. The regression statistics for calibration and prediction, including the correlation coefficient (Rcal2 = 0.9692), root mean square error of calibration (RMSEC = 2.8638), and root mean square error of prediction (RMSEP = 4.0498) (%v/v) for oxygenates content, were calculated. The ACE model showed improved regression results compared to the linear PLS model (Rcal2 = 0.9550, RMSEC = 3.9052, RMSEP = 5.1342) and PCR model (Rcal2 = 0.9160, RMSEC = 6.5330, RMSEP = 7.0270). By applying the ACE technique to the synthetic fully non-linear dataset obtained from the equation y'=exp(y) for the response variable, we demonstrated the power of the ACE algorithm in multivariate analysis and its ability to identify the exact functional relationship between independent and dependent variables to solve fully non-linear problems.

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Photocatalytic methane oxidation to oxygenates with promising performance remains as a grand challenge due to the low productivity and severe overoxidation. Herein, SrWO4 /TiO2 heterojunction was developed for photocatalytic methane oxidation with O2 to liquid oxygenates ( Please replace "oxygenates" with "oxygenated")products under mild reaction conditions. The optimized SrWO4 /TiO2 catalyst exhibited high productivity of 13365 µmol/g with high selectivity of 98.7 % for oxygenates. Benefited from the intimate heterojunction interface of SrWO4 /TiO2 , the constructed I-type heterostructure improved the separation and transfer of photogenerated carriers, and a high-speed transfer channel for photogenerated carriers was fabricated. Simultaneously, the special band structure can increase the amount of photogenerated electrons and holes on the TiO2 surface, which promoted the formation of reactive oxygen species to enhance liquid oxygenates productivity.

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Direct photocatalytic oxidation of methane to liquid oxygenated products is a sustainable strategy for methane valorization at room temperature. However, in this reaction, noble metals are generally needed to function as cocatalysts for obtaining adequate activity and selectivity. Here, we report atomically dispersed nickel anchored on a nitrogen-doped carbon/TiO2 composite (Ni-NC/TiO2 ) as a highly active and selective catalyst for photooxidation of CH4 to C1 oxygenates with O2 as the only oxidant. Ni-NC/TiO2 exhibits a yield of C1 oxygenates of 198 µmol for 4 h with a selectivity of 93 %, exceeding that of most reported high-performance photocatalysts. Experimental and theoretical investigations suggest that the single-atom Ni-NC sites not only enhance the transfer of photogenerated electrons from TiO2 to isolated Ni atoms but also dominantly facilitate the activation of O2 to form the key intermediate ⋅OOH radicals, which synergistically lead to a substantial enhancement in both activity and selectivity.

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Selective oxidation of methane to oxygenates using low-cost and environment-friendly molecular oxygen (O2 ) under mild reaction conditions is a promising strategy but still remains grand challenge. It is of great importance to accelerate the activation of O2 to generate highly active oxygen species, such as hydroxyl peroxide and hydroxyl species to improve catalytic performance for selective oxidation of methane. Selective oxidation of methane using O2 by coupling with in situ generation of hydrogen peroxide via tandem catalysis ensures the easy formation of active oxygen species for methane activation, leading to high oxygenates productivity under mild conditions. In this concept, we summarized the recent progresses for selective oxidation of methane to oxygenates using O2 based on tandem catalysis by coupling with in situ generation of hydrogen peroxide. The remaining challenges and future perspectives for selective oxidation of methane to oxygenates via tandem catalysis were also proposed.

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Due to their high lipid content, microalgae are one of the most significant sources of green hydrocarbons, which might help lessen the world's need for fossil fuels. Many zeolite-based catalysts are quickly deactivated by coke production and have a short lifetime. In this study, a bimetallic Lanthanum-Cerium (La-Ce)-modified HZSM-5 zeolite catalyst was synthesized through an impregnation method and was tested for the conversion of hydrolyzed oil into oxygen-free hydrocarbon fuels of high energy content. Initially, hydrolyzed oil (HO), the byproduct of the transesterification process, was obtained by the reaction of crude oil derived from Chlorella vulgaris microalgae and a methanol. Various catalysts were produced, screened, and evaluated for their ability to convert algal HO into hydrocarbons and other valuable compounds in a batch reactor. The performance of HZSM-5 was systematically tested in view of La-Ce loaded on conversion, yield, and selectivity. NH3-TPD analysis showed that the total acidity of the La-Ce-modified zeolites was lower than that of the pure HZSM-5 catalyst. TGA testing revealed that including the rare earth elements La and Ce in the HZSM-5 catalyst lowered the catalyst propensity for producing coke deposits. The acid sites necessary for algal HO conversion were improved by putting La and Ce into HZSM-5 zeolite at various loading percentages. The maximum hydrocarbon yield (42.963%), the highest HHV (34.362 MJ/Kg), and the highest DOD% (62.191%) were all achieved by the (7.5%La-2.5%Ce)/HZSM-5 catalyst, which was synthesized in this work. For comparison, the hydrocarbon yield for the parent HZSM-5 was 21.838%, the HHV was (33.230 MJ/Kg), and the DOD% was 44.235%. In conclusion, La and Ce-loading on the parent HZSM-5 may be responsible for the observed alterations in textural properties; nevertheless, there is no clear correlation between the physical features and the hydrocarbon yield (%). The principal effect of La and Ce modifying the parent HZSM-5 zeolite was to modify the acidic sites needed to enhance the conversion (%) of the algal HO during the catalytic deoxygenation process, which in turn raised the hydrocarbon yield (%) and increased the HHV and DOD%.

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Despite the extensive research into the catalytic uses of zeolite-based catalysts, these catalysts have a limited useful lifetime because of the deactivating effect of coke production. This study looks at the use of Cerium (Ce) loaded HZSM-5 zeolite catalysts in the hydrocarbon and oxygenated chemical conversion from Chlorella Vulgaris microalgae crude oil. Characterization of structure, morphology, and crystallinity was performed after the catalysts were manufactured using the impregnation technique. Soxhlet extraction was carried out to extract the crude oil of microalgae. Transesterification reaction was used to produce algal hydrolyzed oil (HO), and the resulting HO was put to use in a batch reactor at 300 °C, 1000 rpm, 7 bars of nitrogen pressure, a catalyst to the algal HO ratio of 15% (wt. %), and a retention time of 6 h. To determine which Ce-loaded HZSM-5 catalysts would be most effective in converting algal HO into non-oxygenated molecules (hydrocarbons), we conducted a series of tests. Liquid product characteristics were analyzed for elemental composition, higher heating value (HHV), atomic ratios of O/C and H/C, and degree of deoxygenation (DOD%). Results were categorized into three groups: product yield, chemical composition, and carbon number distribution. When Cerium was added to HZSM-5 zeolite at varying loading percentages, the zeolite's acid sites became more effective in facilitating the algal HO conversion. The results showed that 10%Ce/HZSM-5 had the greatest conversion of the algal HO, the yield of hydrocarbons, HHV, and DOD% (98.2%, 30%, 34.05 MJ/Kg, and 51.44%, respectively) among all the synthesized catalysts in this research. In conclusion, the physical changes seen in the textural characteristics may be attributed to Cerium-loading on the parent HZSM-5; nevertheless, there is no direct association between the physical features and the hydrocarbons yield (%). The primary impact of Cerium alteration of the parent HZSM-5 zeolite was to change the acidic sites required to boost the conversion (%) of the algal HO in the catalytic deoxygenation process, which in turn increased the hydrocarbons yield (%), which in turn increased the HHV and DOD%.

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Microalgae is one of the most important sources of green hydrocarbons because it contains a high percentage of lipids and is likely to reduce reliance on fossil fuels. Several zeolite-based catalysts have a short lifetime due to coke-formation deactivation. In this study, a lanthanum-modified HZSM-5 zeolite catalyst for the conversion of crude oil into non-oxygenated compounds (hydrocarbons) and oxygenated compounds has been investigated. The crude oil of Chlorella Vulgaris microalgae was extracted using Soxhlet and converted into hydrolyzed oil (HO) through a transesterification reaction. The experiments were conducted in a batch reactor (300 °C, 1000 rpm, 7 bar of N2, the catalyst to the algal HO ratio of 15% (wt.%) and 6 h). The results were organized into three groups: product yield, chemical composition, and carbon number distribution. The liquid products were investigated, including their elemental composition, higher heating value (HHV), atomic ratios of O/C and H/C, and degree of deoxygenation (DOD%). The loading of lanthanum into HZSM-5 zeolite with different loading percentages enhanced the acid sites needed for the algal HO conversion. Among all the synthesized catalysts, 10%La/HZSM-5 produced the highest conversion of the algal HO, the highest yield of hydrocarbons, the highest HHV, and the highest DOD%; those were 100%, 36.88%, 34.16 MJ/kg, and 56.11%, respectively. The enhanced catalytic conversion was due to the presence of lanthanum, which alters the active sites for the desired reactions of catalytic deoxygenation. The main effect of the modification of the parent HZSM-5 zeolite with lanthanum led to adjusting the acidic sites needed to increase the conversion (%) of the algal HO in the catalytic deoxygenation process and thus increase the hydrocarbon yield (%), which in turn led to an increase in the HHV and DOD%. The proposed La-based zeolite composite is promising for different energy applications due to its unique benefits compared to other expensive and less-stable catalysts.

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Air quality currently poses a major risk to human health worldwide. Transportation is one of the principal contributors to air pollution due to the quality of exhaust gases. For example, the widely used diesel fuel is a significant source of nitrogen oxides (NOx) and particulate matter (PM). To reduce the content NOx and PM, different oxygenated compounds were mixed into a mineral diesel available at the pump, and their effect on the composition of exhaust gas emissions was measured using a one-cylinder diesel generator. In this setup, adding methanol gave the best relative results. The addition of 2000 ppm of methanol decreased the content of NO by 56%, 2000 ppm of isopropanol decreased NO2 by 50%, and 2000 ppm ethanol decreased PM by 63%. An interesting question is whether it is possible to reduce the impact of hazardous components in the exhaust gas even more by adding oxygenates to biodiesels. In this article, alcohol is added to biodiesel in order to establish the impact on PM and NOx concentrations in the exhaust gases. Adding methanol, ethanol, and isopropanol at concentrations of 2000 ppm and 4000 ppm did not improve NOx emissions. The best results were using pure RME for a low NO content, pure diesel for a low NO2 content, and for PM there were no statistically significant differences.

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The effect of the ZrO2 content on the performance (activity, selectivity, stability) of In2O3-ZrO2 catalyst has been studied on the hydrogenation of CO2/CO mixtures. This effect is a key feature for the viability of using In2O3-ZrO2/SAPO-34 tandem catalysts for the direct conversion of CO2 and syngas into olefins via oxygenates as intermediates. The interest of co-feeding syngas together with CO2 resides in jointly valorizing syngas derived from biomass or wastes (via gasification) and supplying the required H2. The experiments of methanol synthesis and direct synthesis of olefins, with In2O3-ZrO2 and In2O3-ZrO2/SAPO-34 catalysts, respectively, have been carried out under the appropriate conditions for the direct olefins synthesis (400 °C, 30 bar, H2/COX ratio = 3) in an isothermal fixed bed reactor at low space time values (kinetic conditions) to evaluate the behavior and deactivation of the catalysts. The Zr/In ratio of 1/2 favors the conversion of CO2 and COX, attaining good oxygenates selectivity, and prevents the sintering attributable to the over-reduction of the In2O3 (more significant for syngas feeds). The improvement is more remarkable in the direct olefins synthesis, where the thermodynamic equilibrium of methanol formation is displaced, and methanation suppressed (in a greater extent for feeds with high CO content). With the In2O3-ZrO2/SAPO-34 tandem catalysts, the conversion of COx almost 5 folds respect oxygenates synthesis with In2O3-ZrO2 catalyst, meaning the yield of the target products boosts from ∼0.5% of oxygenates to >3% of olefins (selectivity >70%) for mixtures of CO2/COX of 0.5, where an optimum performance has been obtained.

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Direct conversion of methane to high value-added oxygenates under mild conditions has attracted extensive interest. However, the over-oxidation of target products is usually unavoidable due to the easily excessive activation of C-H bond on the sites of supported metal species. Here, we identified the most efficient Zr-oxo nodes of UiO-66 metal-organic frameworks (MOFs) catalysts for the selective oxidation of methane with H2 O2 . These nodes were modified by three types of benzene 1, 4-dicarboxylates (NH2 -BDC, H2 BDC, and NO2 -BDC). Detailed characterizations and DFT calculations revealed that these ligands can effectively tune the electronic properties of Zr-oxo nodes and the H2 BDC ligand led to optimal electronic density of Zr-oxo nodes in UiO-66. Thus the UiO-66-H catalyst promoted the formation of ⋅OH species that adsorbed on Zr-oxo nodes, and facilitated the activation of methane with a lower energy barrier and subsequent conversion to hydroxylation oxygenates with 100 % selectivity.

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Highly selective conversion of methane to oxygenates with O2 as a green oxidant remains a great challenge. It is still difficult to suppress the generation of COx (x=1, 2) as undesired by-products due to unavoidable overoxidation reaction. Hence, tungsten-doped (W-doped) TiO2 photocatalysts were designed with a tunable band structure for photocatalytic oxidation of methane to C1 oxygenates using O2 at low temperature (30 °C). The W-doping effectively modified the electronic and band structure of pristine TiO2 to enhance photocatalytic performance. Liquid oxygenates productivity could reach as high as 12.2 mmol g-1 with high selectivity of 99.4 %. Moreover, COx selectivity was effectively decreased from 21.2 % over TiO2 to 0.6 % for W-doped catalyst. Detailed characterizations further disclosed that W-doping not only enhanced light absorption, but also promoted the separation of photo-generated carriers to improve methane conversion. This work provides new insights into the design of highly efficient photocatalysts for methane oxidation.

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The selective conversion of syngas to higher alcohols is an attractive albeit elusive route in the quest for effective production of chemicals from alternative carbon resources. We report the tandem integration of solid cobalt Fischer-Tropsch and molecular hydroformylation catalysts in a one-pot slurry-phase process. Unprecedented selectivities (>50 wt %) to C2+ alcohols are achieved at CO conversion levels >70 %, alongside negligible CO2 side-production. The efficient overall transformation is enabled by catalyst engineering, bridging gaps in operation temperature and intrinsic selectivity which have classically precluded integration of these reactions in a single conversion step. Swift capture of 1-olefin Fischer-Tropsch primary products by the molecular hydroformylation catalyst, presumably within the pores of the solid catalyst is key for high alcohol selectivity. The results underscore that controlled cooperation between solid aggregate and soluble molecular metal catalysts, which pertain to traditionally dichotomic realms of heterogeneous and homogeneous catalysis, is a promising blueprint toward selective conversion processes.