C1 Species Research Articles

Mechanistic insight into accelerating of light olefin products by surface OH* group on the Fe5C2 catalyst

The conversion of CO2 into high-value-added chemicals via the Fischer-Tropsch Synthesis (FTS) reaction has gathered a lot of attention. The surface oxygenation environment is a significant factor affecting performance of the catalyst. In this work, spin-polarized density-functional theory calculations have been used to investigate the OH* modulation mechanism on CO2 hydrogenation to generate C1 and C2 species. On the pure Fe5C2(510) surface, CH4 is formed through the hydrogenation of dissociated carbon by CO2 activation. At low OH* coverage, the C–C coupling reactions are dramatically promoted compared to methane formation. In addition, CO2 hydrogenation reactions are facilitated by the OH* species, indicating a high activatity and C2+ selectivity. At high OH* coverage, C2 products preferentially form through the CsH2-CdH2* intermediates, contributing to the high selectivity of light olefin products. The results demonstrate that maintaining the surface environment with OH* could be an indispensable measure to obtain the target product in the iron-based CO2 Fischer-Tropsch synthesis system.

Influence of Copper Surfaces on CO2 vs. CO C−C Coupling Efficiency

AbstractCO2 electrochemical reduction (CO2ER) powered by renewable electricity is critical for transitioning to a carbon‐neutral society by transforming CO2 into essential commodities and fuels. The formation of multi‐carbon compounds through C−C coupling reactions is crucial due to their high energy density and broad industrial uses. Traditionally, C−C coupling was believed to occur through the reaction of *CO (surface‐bound CO) with *C1 intermediates (surface‐bound hydrocarbons with one carbon atom produced during CO2ER). In this study, we used DFT calculations combined with a constant electrode potential model to discover a preference for CO2+*C1 over conventional *CO+*C1 coupling on three commonly observed copper surfaces including Cu(111), Cu(110), and Cu(100). This result demonstrates that CO2 is a more efficient carbon source than *CO for coupling with *C1. Among the nine *C1 species investigated, *CHO, *CHOH, *C, *CH, and *CH2 show greater reactivity towards CO2+*C1 couplings on all the surfaces. Thus, enhancing CO2ER efficiency necessitates increasing the surface concentrations of these five *C1 intermediates, and several strategies have been proposed to accomplish this goal.

Asymmetric Cu−N1O3 Sites Coupling Atop‐type and Bridge‐type Adsorbed *C1 for Electrocatalytic CO2‐to‐C2 Conversion

Abstract2D functional porous frameworks offer a platform for studying the structure–activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to breakthrough key limitations on site configuration (typical M−O4 or M−N4 units) and product selectivity (common CO2‐to‐CO conversion). Herein, a novel 2D metal–organic framework (MOF) with planar asymmetric N/O mixed coordinated Cu−N1O3 unit is constructed, labeled as BIT‐119. When applied to CO2RR, BIT‐119 could reach a CO2‐to‐C2 conversion with C2 partial current density ranging from 36.9 to 165.0 mA cm−2 in flow cell. Compared to the typical symmetric Cu−O4 units, asymmetric Cu−N1O3 units lead to the re‐distribution of local electron structure, regulating the adsorption strength of several key adsorbates and the following catalytic selectivity. From experimental and theoretical analyses, Cu−N1O3 sites could simultaneously couple the atop‐type (on Cu site) and bridge‐type (on Cu−N site) adsorption of *C1 species to reach the CO2‐to‐C2 conversion. This work broadens the feasible C−C coupling mechanism on 2D functional porous frameworks.

Metal redispersion strategy for regeneration of sepiolite derived Co-phyllosilicate catalyst during glycerol steam reforming

Metal sintering and coke deposition have become main and irreversible obstacles for catalyst deactivation during H2 production from glycerol steam reforming (GSR). The regenerability of 15Co/SEP catalyst with a phyllosilicate derived strong metal-support interaction (SMSI) was probed by five successive GSR/regeneration cycles in order to evaluate the deactivation process and initial reactivity recovery. Two different regeneration methods were selected for the cycles: redox regeneration and combined regeneration. After the combined regeneration, reproducible GSR behaviors were obtained among the whole cycles. An almost recovery of initial activity (∼94 % of conversion and ∼ 73 % of H2 yield) and 50 h stability was noticed at 15Co/SEP-5 catalyst. By various characterizations analysis of fresh and spent catalysts, it was observed that irreversible metal sintering was aggravated by the redox regeneration, thus provoked initial activity loss and accelerated coking deactivation tendency. The combined regeneration achieved phyllosilicate recrystallization and metal exsolution/redispersion by a combination of NH4F-HNO3 assisted recrystallization and redox treatments, which ensured a small increase in Co0 nanoparticle size (13.2 nm vs. 15.3 nm) and coke deposition (23.9 wt% vs. 27.3 wt%) and inconspicuous change in the C1 species selectivity. The results suggested that 15Co/SEP catalyst is a promising candidate for commercialized GSR due to the favorable regenerability.

Numerical study on laminar burning velocity and ignition delay time of ammonia/methanol mixtures

As a carbon-free hydrogen-carrying fuel, ammonia can effectively alleviate the problem of CO2 emissions and has great application potential in marine engines. The low laminar burning velocity and calorific value, and the narrow flammability limit range make the combustion of pure ammonia difficult. Ammonia/methanol mixed combustion is a feasible method to improve ammonia combustion and mitigate CO2 emissions. It is difficult to accurately predict the laminar burning velocity (LBV) and ignition delay time (IDT) of ammonia/methanol combustion simultaneously by the existing chemical kinetic mechanisms. This study aims to develop a detailed chemical kinetic mechanism that can simultaneously predict the LBV and IDT. The new-developed mechanism was fully validated based on experimental data. Furthermore, it was employed to investigate the effects of methanol blending ratios and equivalence ratios on the LBV and IDT in NH3/CH3OH mixed flames. Besides, chemical kinetic analyses were conducted to elucidate the influence of methanol mixing ratios and equivalence ratios on LBV and IDT. Reaction pathway analysis revealed that the NH3 and CH3OH chemistry interacted by the sharing of H, OH and O radicals in fuels’ decomposition, and chemical interactions of N-containing radicals with the C1 species. The reactions involving C-containing species can notably improve the LBV of NH3/CH3OH mixed combustion. At low equivalence ratio, LBV increases in proportion to the fuel proportion. Conversely, at high equivalence ratio, the effect of oxygen concentration on LBV becomes the dominant factor.

Asymmetric Cu-N1O3 Sites Coupling Atop-type and Bridge-type Adsorbed *C1 for Electrocatalytic CO2-to-C2 Conversion.

2D functional porous frameworks offer a platform for studying the structure-activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to breakthrough key limitations on site configuration (typical M-O4 or M-N4 units) and product selectivity (common CO2-to-CO conversion). Herein, a novel 2D metal-organic framework (MOF) with planar asymmetric N/O mixed coordinated Cu-N1O3 unit is constructed, labeled as BIT-119. When applied to CO2RR, BIT-119 could reach a CO2-to-C2 conversion with C2 partial current density ranging from 36.9 to 165.0 mA cm-2 in flow cell. Compared to the typical symmetric Cu-O4 units, asymmetric Cu-N1O3 units lead to the re-distribution of local electron structure, regulating the adsorption strength of several key adsorbates and the following catalytic selectivity. From experimental and theoretical analyses, Cu-N1O3 sites could simultaneously couple the atop-type (on Cu site) and bridge-type (on Cu-N site) adsorption of *C1 species to reach the CO2-to-C2 conversion. This work broadens the feasible C-C coupling mechanism on 2D functional porous frameworks.

Predicting hydrogenolysis reaction barriers of large hydrocarbons on metal surfaces using machine learning: Implications for polymer deconstruction

Calculating activation energies of chemical reactions for large reaction networks is computationally demanding. Traditional Brønsted-Evans-Polanyi (BEP) relationships are useful in this regard but are prone to substantial estimation errors. Here, we explore machine learning models to predict activation energies for hydrogenolysis reactions on transition metals, including Ru, Pt, and Rh. The curated dataset includes 380 DFT-calculated activation energies of C-C and C-H scission reactions ranging from C1 to C6 species. The mean absolute error of traditional BEPs is 0.30 eV, and published BEPs on smaller hydrocarbons give even larger errors. In comparison, an XGBoost model achieves a mean absolute error of 0.19 eV for the test set without needing additional DFT-calculated energies. The model selects the homologous series among reactions and the electronegativity and atomic mass of the metal atoms as key features. The model appears transferable across metals. This approach can provide accurate and rapid estimation of activation energies of large reaction networks, such as those in plastics recycling, to accelerate catalyst screening. We showcase the impact of hydrocarbon chain length and branching on the barriers, discuss implications for the depolymerization rate of isotactic polypropylene and low vs. high-density polyethylene, and demonstrate the feasibility of hydrogenolysis catalyst screening.

Quantum chemical studies of the reaction mechanisms of enzymatic CO2 conversion.

Enzymatic capture and conversion of carbon dioxide (CO2) into value-added chemicals are of great interest in the field of biocatalysis and have a positive impact on climate change. The quantum chemical methods, recognized as valuable tools for studying reaction mechanisms, have been widely employed in investigating the reaction mechanisms of the enzymes involved in CO2 utilization. In this perspective, we review the mechanistic studies of representative enzymes that are either currently used or have the potential for converting CO2, utilizing the quantum chemical cluster approach and the quantum mechanical/molecular mechanical (QM/MM) method. We begin by summarizing current trends in enzymatic CO2 conversion, followed by a brief description of the computational details of quantum chemical methods. Then, a series of representative examples of the computational modeling of biocatalytic CO2 conversion are presented, including the reduction of CO2 to C1 species (carbon monoxide and formate), and the fixation of CO2 to form aliphatic and aromatic carboxylic acids. The microscopic views of reaction mechanisms obtained from these studies are helpful in guiding the rational design of current enzymes and the discovery of novel enzymes with enhanced performance in converting CO2. Additionally, they provide key information for the de novo design of new-to-nature enzymes. To conclude, we present a perspective on the potential combination of machine learning with quantum description in the study of enzymatic conversion of CO2.

Physiological differences among cryptic species of the Mediterranean crustose coralline alga Lithophyllum stictiforme (Corallinales, Rhodophyta)

ABSTRACT The crustose coralline alga Lithophyllum stictiforme is an important reef builder, forming coralligenous concretions in the Mediterranean Sea. This algal species complex is composed of eight cryptic species (or clades). The objective of our study was to compare light-dependent physiological processes within and between the two most abundant cryptic species (C1 and C4) of L. stictiforme from the Bay of Marseille (France). Physiological rates of respiration, photosynthesis and calcification were measured using incubation chambers under various irradiance levels and in the dark during the summer period. We compared the physiology of the C1 and C4 cryptic species of L. stictiforme among three algal groups: C1 (the most common in the Marseille area) from 28 m depth, C4 from the same site and depth, and C1 from a deeper site at 45 m depth. We found both interspecific (between C1 and C4) and intraspecific (within C1) physiological differences. Photosynthetic parameters showed acclimation to light (or depth) with higher values of initial slope of photosynthetic light response curve (α) and lower values of saturating irradiance (Ek) and compensating irradiance (Ec) for C1 from 45 m than for C1 and C4 from 28 m depth. At the shallower depth, significant physiological differences were observed between C1 and C4 with a higher value of maximum rate of gross photosynthesis (Pg max) in C4, suggesting better ability to grow under high irradiance. Light and dark calcification rates differed only between C4 from 28 m and C1 from 45 m depth, being intermediate in C1 from 28 m depth. On a 24 h basis, diel net calcification rates were significantly higher in specimens from the shallower waters than from the deeper waters. Physiological differences suggest physiological plasticity within the regionally dominant cryptic species C1 and species-specific physiological traits between the cryptic species C1 and C4.

Mechanistic insight into the destruction of perfluoroalkyl acids on gallium oxide

Per- and polyfluoroalkyl substances (PFAS) are a large group of persistent, toxic, and highly water-soluble chemicals resulting from human activities, and their pervasive presence in the environment has garnered global concern. Although accelerating the deconstruction of PFAS is of urgent importance, it still lacks a fundamental understanding of the PFAS mineralization mechanism in photocatalysis. Here, we apply the density functional theory (DFT) calculations to assess the thermodynamic favorability of all possible reaction pathways for two ultrashort perfluoroalkyl acid model compounds (i.e., CF3CF2COO- and CF3CF2SO3-) on β-Ga2O3 surfaces. Our results show that the optimal mineralization pathway includes defluorination and defunctionalization, shortening of the carbon chain, and the mineralization of C1 species, which computationally rationalized many experimental observations of PFAS destruction. This work provides pivotal quantum-level insights into the comprehensive and crucial reaction mechanisms for PFAS degradation, which will facilitate the design of effective catalysts for PFAS mineralization.

Understanding of gas-phase methane pyrolysis towards hydrogen and solid carbon with detailed kinetic simulations and experiments

Methane (CH4) pyrolysis is studied in a tubular flow reactor for the production of hydrogen and solid carbon by combining kinetic modelling, numerical simulation and experiments in a high-temperature flow reactor. Operating conditions are varied such as temperature in the range of 1273–1873 K, hydrogen addition to the feed with a molar H2:CH4 ratio between 0 and 4, and residence time in the range of 3–7 s. Elementary-step reaction mechanisms consisting of pyrolysis and carbon coupling reactions among C1, C2, aromatic and polycyclic aromatic hydrocarbon species are used in the numerical simulations of the species profiles in flow direction. A thermodynamic analysis is performed to acquire the boundary conditions for operation as well to estimate probable by-products (C2H2, C2H4, C2H6, C6H6, C16H10 etc.) over the temperature range. Gas-phase kinetic modelling is performed revealing that CH4 conversion starts at temperatures above 1273 K. Higher temperatures increase CH4 conversion and H2 yield peaking at 1573 K. The cooling temperature gradient downstream of the hot zone in the reactor causes reverse reactions in gas-phase suppressing CH4 conversion. H2 addition to the feed is found to be a crucial parameter for controlling the by-product formation. In the experimental study, a solid carbon yield of 84 % is achieved while gaseous by-products remain less than 1 mol-% at 1673 K, H2:CH4 ratio of 2, and residence time of 5 s. Gas-phase reactions are found to be coupled to surface reactions at higher temperatures.

Increased acylcarnitines in infant heart failure indicate fatty acid oxidation inhibition: towards therapeutic options?

Heart failure in adults is characterized by reduction of long-chain fatty acid oxidation in favour of carbohydrate metabolism. This adaptive phenomenon becomes maladaptive because energy conversion decreases and lipid toxic derivatives known to impair cardiac function are accumulating. No data are available concerning metabolic modification in heart failure in children. In order to evaluate the fatty acid oxidation in children suffering from heart failure, acylcarnitine profiles on dried blood spots were obtained from children under 16years old with dilated cardiomyopathy and clinical heart failure (DCM-HF) and control children. Nine children were included in the DCM-HF group and eight in the control group. Acylcarnitine profiles revealed a significant 3.1-fold increase of total acylcarnitines (sum of C3 to C18 acylcarnitine species) in DCM-HF children compared with controls. This result persisted considering the sum of long-chain acylcarnitines (sum of C14 to C18 species), medium-chain acylcarnitines (sum of C8 to C12 species), and short-chain acylcarnitines (sum of C3 to C6 species), respectively, 2.0-, 2.6-, and 1.9-fold increase compared with the control group. A significant linear correlation was found between left ventricular dilatation or ejection fraction and acylcarnitines accumulation. Finally, acylcarnitine ratio C16OH/C16 and C18OH/C18 enhanced in the DCM-HF group, suggesting a diminution of the long-chain hydroxyl acyl-CoA dehydrogenase activity. Our results suggest down-regulation of fatty acid oxidation in children with heart failure. Such lipidomic alteration could worsen heart function and may suggest considering a metabolic treatment of heart failure in children.

Evaporative emission characteristics of VOCs from in-use light-duty gasoline vehicles

VOCs are an important precursor pollutant of ozone (O3) and secondary organic aerosols (SOA). Vehicle evaporative emission is an essential source of VOCs in urban area, among which lack of localized tests of running loss process in China. This study tested all the evaporative emission processes of in-use light-duty gasoline vehicles (LDGVs), including refueling, running loss, hot soak, and 48-h diurnal breathing loss (DBL) based on the variable temperature Sealed Housing for Evaporative Determination (VT-SHED) of REU (China 4, China 5) vehicles and REC (China 6, with Onboard Refueling Vapor Recovery system) vehicles. The emission factors (EFs), species profiles, Ozone formation potential (OFP), and SOA formation potential (SOAP) of all evaporative emission processes of REU and REC vehicles were obtained. We found that the running loss emissions was less affected by the Onboard Refueling Vapor Recovery (ORVR) system, the average running loss EFs of REU and REC vehicles was 9.386 mg/km; refueling and DBL EFs of REC vehicles was 1.491 mg/L and 0.179 g/day, respectively, 99.8% and 56.0% lower than those of REU vehicles, the hot soak EFs was 0.087 g/h in average. The refueling emissions process was dominated by alkanes (REU: 77.8%; REC: 75.4%), and C4 and C5 species dominated (REU: 75.6%; REC: 67.6%). Among the running loss, hot soak and DBL emissions, alkanes, oxygenated VOCs (OVOCs) and aromatics were the dominant VOCs groups, OVOCs account for a higher proportion in REC vehicles than in REU vehicles. REC vehicles had higher proportion of C1–C3 than REU vehicles, it may be that ORVR has a better adsorption effect on species with large carbon numbers. Running loss VOCs species had a strong correlation with hot soak VOCs species. The OFP of running loss in REU and REC vehicles were 0.9–1.3 and 0.3–0.7 times higher than those of refueling and 48-h DBL, while the SOAP were 10.7–12.9 and both 1.1 times higher, respectively. These findings can provide valuable basis for emission estimation and characteristic analysis for evaporative process of LDGVs and support the development of appropriate pollution-control policy.

Exploring the mechanistic role of alloying elements in copper-based electrocatalysts for the reduction of carbon dioxide to methane.

The promise of electrochemically reducing excess anthropogenic carbon dioxide into useful chemicals and fuels has gained significant interest. Recently, indium-copper (In-Cu) alloys have been recognized as prospective catalysts for the carbon dioxide reduction reaction (CO2RR), although they chiefly yield carbon monoxide. Generating further reduced C1 species such as methane remains elusive due to a limited understanding of how In-Cu alloying impacts electrocatalysis. In this work, we investigated the effect of alloying In with Cu for CO2RR to form methane through first-principles simulations. Compared with pure copper, In-Cu alloys suppress the hydrogen evolution reaction while demonstrating superior initial CO2RR selectivity. Among the alloys studied, In7Cu10 exhibited the most promising catalytic potential, with a limiting potential of -0.54V versus the reversible hydrogen electrode. Analyses of adsorbed geometries and electronic structures suggest that this decreased overpotential arises primarily from electronic perturbations around copper and indium ions and carbon-oxygen bond stability. This study outlines a rational strategy to modulate metal alloy compositions and design synergistic CO2RR catalysts possessing appreciable activity and selectivity.

Soot nucleation in diffusion flames and the role of aromatic hydrocarbons

We perform spatially resolved measurements of light scattering of soot in atmospheric pressure counterflow diffusion flames to complement previously reported data on soot pyrometry, temperature and gaseous species up to three-ring polycyclic aromatic hydrocarbons (PAHs). We compare two flames: a baseline ethylene flame and a toluene-seeded flame in which an aliquot of ethylene in the feed stream is replaced with 3500 ppm of pre-vaporized toluene. The goal is twofold: directly adding an aromatic fuel to bypass the formation of the first aromatic ring, widely regarded as the main bottleneck to soot formation from aliphatic fuels, and assessing the impact of a common component of surrogates of transportation fuels on soot formation. The composition of the fuel and oxidizer streams are adjusted to ensure invariance of the temperature-time history, thereby decoupling the chemical effects of the fuel substitution from other factors. The doping approach enables the comparison of very similar flames with respect to combustion products, radicals and critical precursors to aromatic formation (C2–C5 species), in addition to the temperature-time history. Doping with toluene boosts the aromatic content and soot volume fraction relative to the baseline ethylene flame, but, surprisingly, the soot number density and nucleation rate are affected modestly. As a result, the observed difference in volume fraction in the toluene-doped flame is reflective of larger initial particles at the onset of soot nucleation. The nucleation rate when soot first appears near the flame is of the same order as the dimerization rate of single-ring aromatics, in contrast with the expectation that the dimerization of larger PAHs initiates the process. Even though in and of itself nucleation contributes modestly to the overall soot loading, nucleation conditions the overall soot loading by affecting the size of the initial particle, which ultimately affects subsequent growth.

Microkinetic Simulations of Methanol-to-Olefin Conversion in H-SAPO-34: Dynamic Distribution and Evolution of the Hydrocarbon Pool and Implications for Catalytic Performance

The dominating hydrocarbon pool species (HCPs) in zeolites for methanol-to-olefin (MTO) conversion have been the subject of intense debate for decades due to the diversity of structures and the complexity of reaction networks. We performed microkinetic simulations in a three-site model to study the MTO conversion in industrially relevant H-SAPO-34 zeolite under a wide range of operating conditions. The energetics of 229 and 342 elementary reaction steps were employed, respectively, in the aromatic-based and olefin-based cycles. The dynamic distribution and evolution of the retained aromatic or olefinic HCPs and the origin of olefin products were revealed with respect to reaction conditions. We corroborate that the olefin-based cycle dominates the MTO conversion in H-SAPO-34 under most reaction conditions, and the contribution of the aromatic-based cycle increase with increasing temperature, decreasing pressure, and/or decreasing water partial pressure. The paring route, dedicated highly to propene formation, prevails in the aromatic-based cycle; the side chain route, favoring exclusively ethene formation, only prevails at extremely lower temperatures, higher pressures, and higher water contents. The inherent activity of each aromatic HCP via the paring cycle increases, while its population retained in H-SAPO-34 usually decreases, with the methylation degree remarkably from tetramethylbenzene to hexamethylbenzene. The contents of higher methylbenzenes increase with decreasing water partial pressure, leading to the enhanced contribution of the aromatic-based cycle. The olefin-based cycle contributes to the formation of both ethene and other olefins, and the product distribution is drastically sensitive to reaction conditions. Ethene predominantly comes from the cracking of C5 and C6 species, and propene comes from C5 to C7 species. The olefin-based cycle shifts from the interconversion of C2–C7 olefins toward C2–C5 ones with increasing temperature and water partial pressure to enhance ethene formation. Under industrially relevant conditions, the conversion rate of methanol via the olefin-based cycle is 40-fold greater than that via the aromatic-based cycle (6.6 vs 0.15 s–1), and the former agrees unexpectedly with the experimental value in low-silica AlPO-34 (7.0 s–1). This work thus solves the puzzle of dominating HCPs as a function of reaction conditions in H-SAPO-34 and provides mechanistic insights into the kinetic behaviors, which are the basis for the optimization of the MTO catalyst and process.

Concepts of Computational Approach to Explore Heterogeneous Catalysts for Direct Methane Conversion

AbstractThe nonoxidative coupling of methane has attracted much attention because it yields two useful products: ethane and hydrogen. However, low conversion at low temperatures and carbon deposition at high temperatures are considered problematic. In this Concept article, a solution to these problems is presented. On the basis of the reaction enthalpy for the initial C−H bond cleavage of methane and the energy difference between C1 species (CH3 and CH) on the catalyst surface, a catalyst search guideline is provided to suppress carbon deposition while keeping the conversion rate as high as possible. Alloys are considered catalyst candidates. Few materials satisfy both of these requirements simultaneously; however, several alloys, including MgPt, are shown to be promising. The results of validation experiments for the catalytic performance of MgPt are also discussed.

Detailed Study of the Formation of Soot Precursors and Soot in Highly Controlled Ethylene(/Toluene) Counterflow Diffusion Flames

We perform spatially resolved measurements of temperature, gaseous species up to three-ring Polycyclic Aromatic Hydrocarbons (PAHs), and soot in atmospheric pressure counterflow diffusion flames. First, we characterize fully a baseline ethylene flame and then a toluene-seeded flame in which an aliquot of ethylene in the feed stream is replaced with 3500 ppm of prevaporized toluene. The goal is twofold: to investigate the impact of a common reference fuel component of surrogates of transportation fuels and bypass the main bottleneck to soot formation from aliphatic fuels, that is, the formation of the first aromatic ring. The composition of the fuel and oxidizer streams are adjusted to maintain a constant stoichiometric mixture fraction and global strain rate, thereby ensuring invariance of the temperature-time history in the comparison between the two flames and decoupling the chemical effects of the fuel substitution from other factors. Major combustion products and critical radicals are fixed by the baseline flame, and profiles of critical C2-C5 species precursors to aromatic formation are invariant in both flames. On the other hand, doping with toluene boosts the aromatic content and soot volume fraction, increasing the mole fraction of benzenoid structures and soot volume fraction by a factor of 2 or 3, relative to the baseline ethylene flame. This finding is consistent with the expectation that the formation of the first aromatic ring is no longer a bottleneck to soot formation in the doped flame. In addition, toluene bypasses completely benzene formation, opening a radical recombination pathway to soot precursors through the production of C14H14 (via dimerization of benzyl radical) and pyrene (through dimerization of indenyl radical).

Activity Enhancement of PtIr Catalysts for Complete Ethanol Oxidation Reaction by Tuning C–O Coupling Abilities

Designing efficient catalysts for the complete ethanol oxidation reaction (EOR) remains challenging because of its complex reaction network, which involves more than 70 reactions of C2 species, many reactions of C1 species, water dissociation, as well as reactions leading to by-products. Recently, the promising EOR performance of the one-atom-thick Ir-rich skin of a bimetallic PtIr electrocatalyst was illustrated and its further improvement requires a thorough understanding of the complete EOR mechanism that is still largely lacking. Therefore, we studied 58 critical elementary reactions of complete EOR including all three stages of catalysis of ethanol oxidation, i.e., dehydrogenation, C–C bond cleavage, and CO2 formation, as well as including water dissociation, on three (100)-exposed layered bimetallic Pt–Ir catalysts using density functional theory (DFT) calculations. Based on the activation and reaction energies, we mapped out the mechanisms of complete EOR on these layered PtIr catalysts. The DFT results demonstrated that the different C–O coupling abilities of the catalyst plays a leading role in the complete EOR performance of Pt–Ir catalysts. We further performed DFT studies on the reactions on a Ir@Pt(100) surface with about 6% Pt atoms on the Ir layer. The surface Pt atoms exhibit excellent C–O coupling of C1 species (e.g., CO + O → CO2), while the Ir atoms prevent the C–OH coupling to form CH3COOH (CH3CO + OH → CH3COOH). Both DFT and kinetics studies indicate that the Ir@Pt(100) surface with Pt-doped active sites is the best for complete EOR and is responsible for the experimentally observed high catalytic performance. This work indicates effective EOR catalysis need to go beyond single metal catalysts and the core–shell structures of multimetallic catalysts.

Ultrathin ZnIn2S4 nanosheet arrays activated by nitrogen-doped carbon for electrocatalytic CO2 reduction reaction toward ethanol

Ternary ZnIn2S4 (ZIS) is a kind of potential electrocatalyst for CO2 reduction reaction (CO2RR). However, the reported reduction products are usual C1 species. Considering that N doped carbon can increase adsorption of CO2 molecules, facilitate electron transfer, and activate active sites, here ultrathin ZIS nanosheet arrays (ZIS NSAs) grown on N doped carbon cloth (NDCC) were synthesized through a facile hydrothermal route. The as-synthesized ZIS NSAs/NDCC enabled electrocatalytic CO2RR toward ethanol with the highest 42 % faradaic efficiency (FE) at an applied potential of − 0.7 V versus the reversible hydrogen electrode (RHE) in CO2-saturated 0.5 M KHCO3 aqueous solution. This is first report on ZIS-based electrocatalyst for electrocatalytic CO2RR toward ethanol production. The experimental results and density functional theory (DFT) calculations showed that NDCC could enhance the CO2RR activity and promote CO-CO coupling process. Our work not only provides a new electrocatalyst for CO2RR to ethanol but also stresses the influence of N doped carbon substrate and bimetallic effect on electrocatalytic CO2RR.