Construction of Au quantum dots/nitrogen-defect-enriched graphite carbon nitride heterostructure via photo-deposition towards enhanced nitric oxide photooxidation.

The challenge of mitigating pollution stemming from industrial exhaust emissions is a pressing issue in both academia and industry. This study presents the successful synthesis of nitrogen-defect-enriched graphite carbon nitride (g-C3N4) using a two-step calcination technique. Furthermore, a g-C3N4-Au heterostructure was fabricated through the photo-deposited Au quantum dots (QDs). When subjected to visible light irradiation, this heterostructure exhibited robust nitric oxide (NO) photooxidation activity and stability. With its fluffy, porous structure and large surface area, the nitrogen-defect-enriched g-C3N4 provides more active sites for photooxidation processes. The ability of g-C3N4 to absorb visible light is enhanced by the local surface plasmon resonance (LSPR) effect of Au QDs. Additionally, the lifetime of photogenerated charge carriers is extended by the presence of N defects and Au, which effectively prevent photogenerated electron-hole pairs from recombining during the photooxidation process. Moreover, the oxidation pathway of NO was analyzed through In-situ Fourier transform infrared (FT-IR) spectroscopy and Density Functional Theory (DFT) calculation. Computational findings revealed that the introduction of Au QDs decreases the activation energy of the oxidation reaction, thereby facilitating its occurrence while diminishing the formation of intermediate products. As a result, NO is predominantly converted to nitrate (NO3-). This work unveils a novel approach to constructing semiconductor-cocatalyst heterostructures and elucidates their role in NO photooxidation.

Liquid metals for boosting stability of zeolite catalysts in the conversion of methanol to hydrocarbons.

Methanol-to-hydrocarbons (MTH) process has been considered one of the most practical approaches for producing value-added products from methanol. However, the commonly used zeolite catalysts suffer from rapid deactivation due to coke deposition and require regular regeneration treatments. We demonstrate that low-melting-point metals, such as Ga, can effectively promote more stable methanol conversion in the MTH process by slowing coke deposition and facilitating the desorption of carbonaceous species from the zeolite. The ZSM-5 zeolite physically mixed with liquid gallium exhibited an enhanced lifetime in the MTH reaction, which increased by a factor of up to ~14 as compared to the parent ZSM-5. These results suggest an alternative route to the design and preparation of deactivation-resistant zeolite catalysts.

Boosting Gas-Phase TiO2 Photocatalysis with Weak Electric Field Strengths of Volt/Centimeter.

Among semiconductor nanomaterials, titanium dioxide is at the forefront of heterogeneous photocatalysis, but its catalytic activity greatly suffers from the loss of photoexcited charge carriers through deleterious recombination processes. Here, we investigate the impact of an external electric field (EEF) applied to conventional P25 TiO2 nanopowder with or without Au nanoparticles (NPs) to circumvent this issue. The study of two redox reactions in the gas phase, water splitting and toluene degradation, reveals an enhancement of the photocatalytic activity with rather modest electric fields of a few volt/centimeters only. Such an improvement arises from the electric-field-induced quenching of the green emission in anatase, allowing the photoexcited charge carriers to be transferred to the adsorbed reactants instead of pointless radiative recombinations. Applying an EEF across a trap-rich metal oxide material, such as TiO2, which, when impregnated with Au NPs, leads, respectively, to 12- and 6-fold enhancements in the production of hydrogen and the oxidation of toluene for an electric field of 8 V/cm, without any electrolysis, is a simple and elegant strategy to meet higher photocatalytic efficiencies.

The Impact of Oxygen Surface Coverage and Carbidic Carbon on the Activity and Selectivity of Two-Dimensional Molybdenum Carbide (2D-Mo2C) in Fischer-Tropsch Synthesis.

Transformations of oxygenates (CO2, CO, H2O, etc.) via Mo2C-based catalysts are facilitated by the high oxophilicity of the material; however, this can lead to the formation of oxycarbides and complicate the identification of the (most) active catalyst state and active sites. In this context, the two-dimensional (2D) MXene molybdenum carbide Mo2CTx (Tx are passivating surface groups) contains only surface Mo sites and is therefore a highly suitable model catalyst for structure-activity studies. Here, we report that the catalytic activity of Mo2CTx in Fischer-Tropsch (FT) synthesis increases with a decreasing coverage of surface passivating groups (mostly O*). The in situ removal of Tx species and its consequence on CO conversion is highlighted by the observation of a very pronounced activation of Mo2CTx (pretreated in H2 at 400 °C) under FT conditions. This activation process is ascribed to the in situ reductive defunctionalization of Tx groups reaching a catalyst state that is close to 2D-Mo2C (i.e., a material containing no passivating surface groups). Under steady-state FT conditions, 2D-Mo2C yields higher hydrocarbons (C5+ alkanes) with 55% selectivity. Alkanes up to the kerosine range form, with value of α = 0.87, which is ca. twice higher than the α value reported for 3D-Mo2C catalysts. The steady-state productivity of 2D-Mo2C to C5+ hydrocarbons is ca. 2 orders of magnitude higher relative to a reference ß-Μo2C catalyst that shows no in situ activation under identical FT conditions. The passivating Tx groups of Mo2CTx can be reductively defunctionalized also by using a higher H2 pretreatment temperature of 500 °C. Yet, this approach leads to a removal of carbidic carbon (as methane), resulting in a 2D-Mo2C1-x catalyst that converts CO to CH4 with 61% selectivity in preference to C5+ hydrocarbons that are formed with only 2% selectivity. Density functional theory (DFT) results attribute the observed selectivity of 2D-Mo2C to C5+ alkanes to a higher energy barrier for the hydrogenation of surface alkyl species relative to the energy barriers for C-C coupling. The removal of O* is the rate-determining step in the FT reaction over 2D-Mo2C, and O* is favorably removed in the form of CO2 relative to H2O, consistent with the observation of a high CO2 selectivity (ca. 50%). The absence of other carbon oxygenates is explained by the energetic favoring of the direct over the hydrogen-assisted dissociative adsorption of CO.

Direct Photocatalytic Synthesis of Acetic Acid from Methane and CO at Ambient Temperature Using Water as Oxidant.

Direct functionalization of methane selectively to value-added chemicals is still one of the main challenges in modern science. Acetic acid is an important industrial chemical produced nowadays by expensive and environmentally unfriendly carbonylation of methanol using homogeneous catalysts. Here, we report a new photocatalytic reaction route to synthesize acetic acid from CH4 and CO at room temperature using water as the sole external oxygen source. The optimized photocatalyst consists of a TiO2 support and ammonium phosphotungstic polyoxometalate (NPW) clusters anchored with isolated Pt single atoms (Pt1). It enables a stable synthesis of 5.7 mmol·L-1 acetic acid solution in 60 h with the selectivity over 90% and 66% to acetic acid on liquid-phase and carbon basis, respectively, with the production of 99 mol of acetic acid per mol of Pt. Combined isotopic and in situ spectroscopy investigation suggests that synthesis of acetic acid proceeds via a photocatalytic oxidative carbonylation of methane over the Pt1 sites, with the methane activation facilitated by water-derived hydroxyl radicals.

Light olefin synthesis from a diversity of renewable and fossil feedstocks: state-of the-art and outlook.

Light olefins are important feedstocks and platform molecules for the chemical industry. Their synthesis has been a research priority in both academia and industry. There are many different approaches to the synthesis of these compounds, which differ by the choice of raw materials, catalysts and reaction conditions. The goals of this review are to highlight the most recent trends in light olefin synthesis and to perform a comparative analysis of different synthetic routes using several quantitative characteristics: selectivity, productivity, severity of operating conditions, stability, technological maturity and sustainability. Traditionally, on an industrial scale, the cracking of oil fractions has been used to produce light olefins. Methanol-to-olefins, alkane direct or oxidative dehydrogenation technologies have great potential in the short term and have already reached scientific and technological maturities. Major progress should be made in the field of methanol-mediated CO and CO2 direct hydrogenation to light olefins. The electrocatalytic reduction of CO2 to light olefins is a very attractive process in the long run due to the low reaction temperature and possible use of sustainable electricity. The application of modern concepts such as electricity-driven process intensification, looping, CO2 management and nanoscale catalyst design should lead in the near future to more environmentally friendly, energy efficient and selective large-scale technologies for light olefin synthesis.

Synthesis of stack plate covalent organic framework nanotubes using a self-assembled acid as a soft template.

COF-LZU1 with nanotube-like morphology has been synthesized with high crystallinity and pore volume in the presence of trimesic acid as a template. The as-synthesized COF nanotubes consist of a stack of plates with a diameter of about 100 nm with a hollow channel inside of about 20 nm.

Lignin Compounds to Monoaromatics: Selective Cleavage of C-O Bonds over a Brominated Ruthenium Catalyst.

The cleavage of C-O linkages in aryl ethers in biomass-derived lignin compounds without hydrogenation of the aromatic rings is a major challenge for the production of sustainable mono-aromatics. Conventional strategies over the heterogeneous metal catalysts require the addition of homogeneous base additives causing environmental problems. Herein, we propose a heterogeneous Ru/C catalyst modified by Br atoms for the selective direct cleavage of C-O bonds in diphenyl ether without hydrogenation of aromatic rings reaching the yield of benzene and phenol as high as 90.3 % and increased selectivity to mono-aromatics (97.3 vs. 46.2 % for initial Ru) during depolymerization of lignin. Characterization of the catalyst indicates selective poisoning by Br of terrace sites over Ru nanoparticles, which are active in the hydrogenation of aromatic rings, while the defect sites on the edges and corners remain available and provide higher intrinsic activity in the C-O bond cleavage.

Carbon-based catalysts for Fischer-Tropsch synthesis.

Fischer-Tropsch synthesis (FTS) is an essential approach to convert coal, biomass, and shale gas into fuels and chemicals, such as lower olefins, gasoline, diesel, and so on. In recent years, there has been increasing motivation to deploy FTS at commercial scales which has been boosting the discovery of high performance catalysts. In particular, the importance of support in modulating the activity of metals has been recognized and carbonaceous materials have attracted attention as supports for FTS. In this review, we summarised the substantial progress in the preparation of carbon-based catalysts for FTS by applying activated carbon (AC), carbon nanotubes (CNTs), carbon nanofibers (CNFs), carbon spheres (CSs), and metal-organic frameworks (MOFs) derived carbonaceous materials as supports. A general assessment of carbon-based catalysts for FTS, concerning the support and metal properties, activity and products selectivity, and their interactions is systematically discussed. Finally, current challenges and future trends in the development of carbon-based catalysts for commercial utilization in FTS are proposed.

Mobility and versatility of the liquid bismuth promoter in the working iron catalysts for light olefin synthesis from syngas.

Liquid metals are a new emerging and rapidly growing class of materials and can be considered as efficient promoters and active phases for heterogeneous catalysts for sustainable processes. Because of low cost, high selectivity and flexibility, iron-based catalysts are the catalysts of choice for light olefin synthesis via Fischer-Tropsch reaction. Promotion of iron catalysts supported by carbon nanotubes with bismuth, which is liquid under the reaction conditions, results in a several fold increase in the reaction rate and in a much higher light olefin selectivity. In order to elucidate the spectacular enhancement of the catalytic performance, we conducted extensive in-depth characterization of the bismuth-promoted iron catalysts under the reacting gas and reaction temperatures by a combination of cutting-edge in situ techniques: in situ scanning transmission electron microscopy, near-atmospheric pressure X-ray photoelectron spectroscopy and in situ X-ray adsorption near edge structure. In situ scanning transmission electron microscopy conducted under atmospheric pressure of carbon monoxide at the temperature of catalyst activation showed iron sintering proceeding via the particle migration and coalescence mechanism. Catalyst activation in carbon monoxide and in syngas leads to liquid bismuth metallic species, which readily migrate over the catalyst surface with the formation of larger spherical bismuth droplets and iron-bismuth core-shell structures. In the working catalysts, during Fischer-Tropsch synthesis, metallic bismuth located at the interface of iron species undergoes continuous oxidation and reduction cycles, which facilitate carbon monoxide dissociation and result in the substantial increase in the reaction rate.

The Fischer-Tropsch reaction in the aqueous phase over rhodium catalysts: a promising route to selective synthesis and separation of oxygenates and hydrocarbons.

In the present communication, we uncovered the aqueous phase Fischer-Tropsch reaction over rhodium catalysts. The reaction results in the synthesis and consecutive separation of hydrocarbons and oxygenates into two phases. Use of a rhodium Schiff base complex as a precursor for catalyst preparation allows efficient control of the Rh metal nanoparticle size distribution and leads to higher alcohol selectivity.

Selective photocatalytic conversion of methane into carbon monoxide over zinc-heteropolyacid-titania nanocomposites.

Chemical utilization of vast fossil and renewable feedstocks of methane remains one of the most important challenges of modern chemistry. Herein, we report direct and selective methane photocatalytic oxidation at ambient conditions into carbon monoxide, which is an important chemical intermediate and a platform molecule. The composite catalysts on the basis of zinc, tungstophosphoric acid and titania exhibit exceptional performance in this reaction, high carbon monoxide selectivity and quantum efficiency of 7.1% at 362 nm. In-situ Fourier transform infrared and X-ray photoelectron spectroscopy suggest that the catalytic performance can be attributed to zinc species highly dispersed on tungstophosphoric acid /titania, which undergo reduction and oxidation cycles during the reaction according to the Mars-van Krevelen sequence. The reaction proceeds via intermediate formation of surface methyl carbonates.

Alkyl coupling in tertiary amines as analog of Guerbet condensation reaction.

We report here that C-C coupling in tertiary amines for the synthesis of long chain and hindered amines might be efficiently performed over Pt and Pd catalysts. The mechanism study confirms similarity with the Guerbet reaction through dehydrogenation of the alkyl group and subsequent attack of the α-carbon atom by an alkyl group of another molecule. Finally, secondary amines and tertiary amines with longer alkyl chains are formed.

Design of core-shell titania-heteropolyacid-metal nanocomposites for photocatalytic reduction of CO2 to CO at ambient temperature.

The photocatalytic conversion of CO2 not only reduces the greenhouse effect, but also provides value-added solar fuels and chemicals. Herein, we report the design of new efficient core-shell nanocomposites for selective photocatalytic CO2 to CO conversion, which occurs at ambient temperature. A combination of characterization techniques (TEM, STEM-EDX, XPS, XRD, FTIR photoluminescence) indicates that the CO2 reduction occurs over zinc species highly dispersed on the heteropolyacid/titania core-shell nanocomposites. These core-shell structures create a semiconductor heterojunction, which increases charge separation and the lifetime of charge carriers' and leads to higher electron flux. In situ FTIR investigation of the reaction mechanism revealed that the reaction involved surface zinc bicarbonates as key reaction intermediates. In a series of catalysts containing noble and transition metals, zinc phosphotungstic acid-titania nanocomposites exhibit high activity reaching 50 µmol CO g-1 h-1 and selectivity (73%) in the CO2 photocatalytic reduction to CO at ambient temperature. The competitive water splitting reaction has been significantly suppressed over the Zn sites in the presence of CO2.

Tuning Zeolite Properties for a Highly Efficient Synthesis of Propylene from Methanol.

A series of nanosized ZSM-5 samples was synthesized at 170, 150, 120, and 100 °C. Experimental data show that the decrease of crystallization temperature leads to significant changes in zeolite properties. Crystals synthesized at 100 °C exhibit many framework defects with lower acid-site density, strength, and a larger external surface area. The selectivity to light olefins and the propylene-to-ethylene ratio increases as the crystallization temperature decreases. A propylene-to-ethylene ratio of above 6 with the highest selectivity to propylene of 53 % was obtained over ZSM-5 catalyst prepared at 100 °C. The stability of the nanosized zeolite in methanol to olefins (MTO) was also improved compared to the industrial sample with a similar Si/Al ratio. This catalytic performance is a result of the decrease in the acid-site density, strength, and the crystals' size, providing a shorter diffusion path and larger external surface area. The presence of structural defects and a different external surface in the crystals has been shown to play an important role in the MTO catalyst performance.

Selective Electrogenerative Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandialdehyde.

2,5-furandialdehyde (DFF) was synthesized by electrogenerative oxidation of 5-hydroxymethylfurfural (HMF) over a PtRu catalyst with 89 % selectivity at 50 °C after 17 h. This approach opens an avenue for a selective, energy-efficient and green oxidation of biomass-derived platform alcohols to added-value chemicals.

"Fishing" of heteropolyacids into carbonaceous seine via coking.

The carbon encapsulated tungstophosphoric acid was synthesized by the controlled coking during gas phase reaction of formaldehyde with isobutene. The as-made material showed unique stability toward leaching in the aqueous phase due to localization of HPA clusters inside the porous coke matrix with high activity in the esterification reaction.

Design of a metal-promoted oxide catalyst for the selective synthesis of butadiene from ethanol.

The synthesis of buta-1,3-diene from ethanol has been studied over metal-containing (M=Ag, Cu, Ni) oxide catalysts (MO(x)=MgO, ZrO2, Nb2O5, TiO2, Al2O3) supported on silica. Kinetic study of a wide range of ethanol conversions (2-90%) allowed the main reaction pathways leading to butadiene and byproducts to be determined. The key reaction steps of butadiene synthesis were found to involve ethanol dehydrogenation, acetaldehyde condensation, and the reduction of crotonaldehyde with ethanol into crotyl alcohol. Catalyst design included the selection of active components for each key reaction step and merging of these components into multifunctional catalysts and adjusting the catalyst functions to achieve the highest selectivity. The best catalytic performance was achieved over the Ag/ZrO2/SiO2 catalyst, which showed the highest selectivity towards butadiene (74 mol%).

Selective production of methane from aqueous biocarbohydrate streams over a mixture of platinum and ruthenium catalysts.

A one-step process for the selective production of methane from low-value aqueous carbohydrate streams is proposed. Sorbitol, used herein as a model compound, is fully converted to methane, CO2 , and a minor amount of H2 by using a physical mixture of Pt and Ru (1:5 in mass basis) at 220 °C and 35 bar. This conversion is the result of hydrogenolysis of part of the sorbitol over Ru and the in situ production of H2 through the aqueous-phase reforming of the remaining carbohydrate over Pt. A synergistic effect of the combination of these two catalysts results in the rapid and highly selective conversion of the carbohydrate to methane. This process offers the possibility of upgrading a low-value carbohydrate stream into a valuable fuel with no addition of H2. Exergy analysis reveals that nearly 80 % of the exergy of the reactant is recovered as methane.

Catalysis by coke deposits: synthesis of isoprene over solid catalysts.

A help rather than a hindrance: Carbonaceous deposits have been found to play a key role in the selective synthesis of isoprene from formaldehyde and isobutene over solid catalysts. They accumulate on the catalyst surface during the induction period and promote the interaction of the substrates at the steady state. The proposed mechanism shows the way forward for the design of efficient solid catalysts for the synthesis of isoprene.