Catalytic Conversion Research Articles

An improved boron-catalyzed cycloaddition of CO2 to epoxides for the production of five-membered cyclic carbonates under atmospheric versus high-pressure conditions

A series of novel boron-based compounds (boronate esters) (1–8) were designed and successfully synthesized by introducing 3-(bromomethyl)phenylboronic acid into the various cis-diols using a Dean-Stark trap to remove the water formed during the esterification reactions. The synthesized boron-based compounds were characterized by 1H, 13C, and 11B NMR, FT-IR, UV–Vis, LC-MS/MS, elemental analysis, TGA-DTA, and melting point measurement techniques. Additionally, the Lewis acidity of the synthesized boronate esters was investigated by the conventional Gutmann-Beckett test. After the boronate esters were characterized in detail by various spectroscopic techniques, these compounds have been used as organocatalysts for the highly efficient conversion of greenhouse gas CO2 to cyclic carbonates under atmospheric versus high-pressure conditions without any solvents. The best conversion was performed in the presence of an organoboron catalyst (3) and DMAP as cocatalyst, with a 90.0 % yield and 97.7 % selectivities under high reactor pressure and with a 45.2% yield and 97.4% selectivities under atmospheric conditions. In addition, after it was determined that the target organoboron catalysts showed high catalytic activity, the effects of epoxide, base, temperature, CO2 pressure, Lewis acidity, reaction time, and amount of catalyst and base on the catalytic conversion were investigated for these catalysts.

Weakening Mn-O Bond Strength in Mn-Based Perovskite Catalysts to Enhance Propane Catalytic Combustion.

Exploring highly efficient and robust non-noble metal catalysts for VOC abatement is crucial but challenging. Mn-based perovskites are a class of redox catalysts with good thermal stability, but their activity in the catalytic combustion of light alkanes is insufficient. In this work, we modulated the Mn-O bond strength in a Mn-based perovskite via defect engineering, over which the catalytic activity of propane combustion was significantly enhanced. It demonstrates that the oxygen vacancy concentration and the Mn-O bond strength can be efficiently modulated by finely tuning the Ni content in SmNixMn1-xO3 perovskite catalysts (SNxM1-x), which in turn can enhance the redox ability and generate more active oxygen species. The SN0.10M0.90 catalyst with the lowest Mn-O bond strength exhibits the lowest apparent activation energy, over which the propane conversion rate increases by 3.6 times compared to that on the SmMnO3 perovskite catalyst (SM). In addition, a SN0.10M0.90/cordierite monolithic catalyst can also exhibit a remarkable catalytic performance and deliver excellent long-term durability (1000 h), indicating broad prospects in industrial applications. Moreover, the promotional effect of Ni substitution was further unveiled by density functional theory (DFT) calculations. This work brings a favorable guidance for the exploration of highly efficient perovskite catalysts for light alkane elimination.

Rare Earth Single-Atom Catalysis for High-Performance Li-S Full Battery with Ultrahigh Capacity.

Lithium-sulfur (Li-S) batteries have many advantages but still face problems such as retarded polysulfides redox kinetics and Li dendrite growth. Most reported single atom catalysts (SACs) for Li-S batteries are based on d-band transition metals whose d orbital constitutes active valence band, which is inclined to occur catalyst passivation. SACs based on 4f inner valence orbital of rare earth metals are challenging for their great difficulty to be activated. In this work, we design and synthesize the first rare earth metal Sm SACs which has electron-rich 4f inner orbital to promote catalytic conversion of polysulfides and uniform deposition of Li. Sm SACs enhance the catalysis by the activated 4f orbital through an f-d-p orbital hybridization. Using Sm-N3C3 modified separators, the half cells deliver a high capacity over 600 mAh g-1 and a retention rate of 84.3% after 2000 cycles. The fabricated S/CNTs|Sm-N3C3@PP|Sm-N3C3-Li full batteries can provide an ultra-stable cycling performance of a retention rate of 80.6% at 0.2 C after 100 cycles, one of the best full Li-S batteries. This work provides a new perspective for the development of rare earth metal single atom catalysis in electrochemical reactions of Li-S batteries and other electrochemical systems for next-generation energy storage.

Rare Earth Single‐Atom Catalysis for High‐Performance Li−S Full Battery with Ultrahigh Capacity

Lithium‐sulfur (Li−S) batteries have many advantages but still face problems such as retarded polysulfides redox kinetics and Li dendrite growth. Most reported single atom catalysts (SACs) for Li−S batteries are based on d‐band transition metals whose d orbital constitutes active valence band, which is inclined to occur catalyst passivation. SACs based on 4f inner valence orbital of rare earth metals are challenging for their great difficulty to be activated. In this work, we design and synthesize the first rare earth metal Sm SACs which has electron‐rich 4f inner orbital to promote catalytic conversion of polysulfides and uniform deposition of Li. Sm SACs enhance the catalysis by the activated 4f orbital through an f‐d‐p orbital hybridization. Using Sm‐N3C3 modified separators, the half cells deliver a high capacity over 600 mAh g−1 and a retention rate of 84.3% after 2000 cycles. The fabricated S/CNTs|Sm‐N3C3@PP|Sm‐N3C3‐Li full batteries can provide an ultra‐stable cycling performance of a retention rate of 80.6% at 0.2 C after 100 cycles, one of the best full Li−S batteries. This work provides a new perspective for the development of rare earth metal single atom catalysis in electrochemical reactions of Li−S batteries and other electrochemical systems for next‐generation energy storage.

Hierarchical Co-doped hollow Ti3C2Tx tubes with built-in electron/ion transport network for high-performance lithium sulfur batteries

A crucial approach to enhancing the electrochemical performance of lithium-sulfur batteries (LSBs) is to develop a dependable sulfur host material possessing reasonable structure, high electrical conductivity, and exceptional adsorption/catalytic capabilities towards lithium polysulfides (LiPSs). Herein, Co-doped hollow Ti3C2Tx tubes with in-situ grown CNTs as a built-in electron/ion transport network (HTCTs/Co/CNTs) are prepared via electrospinning technique combined with the self-catalyzed growth strategy. The unique hierarchical porous structure of HTCTs/Co/CNTs not only increases the sulfur loading and alleviates the volume expansion, but also effectively suppresses the shuttling effect of LiPSs through the synergism between physical confinement and chemical adsorption. It is revealed that the combination of Ti3C2Tx MXene and metallic Co enhances the LiPSs absorbability and accelerates the catalytic conversion of sulfur species, thereby improving sulfur utilization and electrochemical reversibility. The corresponding cells with HTCTs/Co/CNTs/S cathode retain high capacities of 901.9 mAh g−1 after 100 cycles at 0.2 C and 725.9 mAh g−1 after 500 cycles at 1.0 C. More importantly, a high areal capacity of 4.83 mAh cm−2 is achieved under a high sulfur loading of 5.8 mg cm−2 and a low E/S ratio of 4.3 µL mg−1 after 50 cycles at 0.1 C.

First-principles insights into the mechanism of CO2hydrogenation reactions by Fe-PNP pincer complex.

Using the state of the art theoretical methods, we have provided a comprehensive mechanistic understanding of the CO2 hydrogenation into HCOOH, H2CO, andCH3OH by 2,6-bis(diisopropylphosphinomethyl)pyridine (PNP)-ligated Fe pincer complex, featuring one CO and two H as co-ligands. For the computational investigation,a verified structural model containing methyl groups in place of the experimental isopropyl groups was used. Three catalytic conversions involving hydrogenation of CO2into formic acid (HCOOH), HCOOH into formaldehyde and methanol were studied indifferent solvent medium. Our modelled complex appears to be a viable base-free catalyst for the conversion of CO2 into HCOOH and HCOOH into H2CO, based on the freeenergy profiles, which show apparent activation energy barriers of 16.28 kcal/mol and23.63 kcal/mol for the CO2 to HCOOH and HCOOH to H2CO conversion, respectively. However, the computed results show that, due to the huge energy span of H2CO toCH3OH conversion, complete hydrogenation of CO2 into methanol could not occur under moderate conditions. Morpholine co-catalyst, which can lower the hydrogenationbarrier by taking part in a simultaneous H-atom donation-acceptance process, couldhave assisted in completing this step.

The Affects of Ce Doping Cr\(_2\)O\(_3\) Based Catalysts Supported on Activated Carbon for 1,2-Dichloroethane Abatement

Hydrothermal method is used to prepare activated carbon (AC) supported chromium-based catalysts for the catalytic combustion of 1,2-dichloroethane (DCE). The physicochemical properties relating catalysts are evaluated by several characterization techniques such as XRD, SEM, XPS, N2 adsorption-desorption isotherms, H2-TPR and NH3-TPR. The outcomes demonstrated that the Cr2O3 is the perfect targeted base catalyst adding to the facts that the hydrothermal approach is an appropriate way to create catalysts with superior properties. The textural characteristics, reducibility, and acidity of the Cr-based catalysts were all enhanced by the addition of cerium (Ce) and AC. Nevertheless, the research shows how crucial the Ce doping amount is for adjusting the physicochemical characteristics and catalytic efficacy of Cr-based catalysts. The catalyst 20Ce-Cr/AC has the maximum catalytic activity when it came to DCE combustion, where its T50 and T90 attaining of 247°C and 269.5°C, correspondingly. This is explained by the ideal Ce doping level, which improves the redox characteristics and revealed more active sites.

Ni-based Catalyst Development for the Catalytic Conversion of CO2 to Substitute Natural Gas—Effect of Preparation Method

Ni-based Catalyst Development for the Catalytic Conversion of CO2 to Substitute Natural Gas—Effect of Preparation Method

Performance of ammonia catalytic combustion over Cu-CeOx catalyst and the impact of oxygen concentration

Ammonia has long been regarded as a high-quality zero-carbon fuel; however, limitations in its combustion characteristics have restricted its practical applications. Catalytic combustion is considered an effective solution to overcome the challenges associated with ammonia combustion. In this study, we successfully synthesized a copper-cerium binary catalyst (Cu-CeOx) using the sol-gel method, demonstrating outstanding performance for NH3 catalytic combustion. Through in-situ DRIFTS results, we observed that the 15Cu-CeOx catalyst exhibits both i-SCR and -NH mechanisms. The oxygen concentration affects the N2 selectivity by modulating the overoxidation of NH3. Under high oxygen concentrations, high temperatures promote the excessive oxidation of NH3, and ammonia combustion through the i-SCR mechanism. Conversely, the oxygen concentration was equal to NH3 reaction stoichiometry, the overoxidation of NH3 is limited, and ammonia combustion proceeds through the NH mechanism, resulting in higher N2 selectivity.

MOFs-Based Materials with Confined Space: Opportunities and Challenges for Energy and Catalytic Conversion.

Metal-Organic Frameworks (MOFs) are a very promising material in the fields of energy and catalysis due to their rich active sites, tunable pore size, structural adaptability, and high specific surface area. The concepts of "carbon peak" and "carbon neutrality" have opened up huge development opportunities in the fields of energy storage, energy conversion, and catalysis, and have made significant progress and breakthroughs. In recent years, people have shown great interest in the development of MOFs materials and their applications in the above research fields. This review introduces the design strategies and latest progress of MOFs are included based on their structures such as core-shell, yolk-shell, multi-shelled, sandwich structures, unique crystal surface exposures, and MOF-derived nanomaterials in detail. This work comprehensively and systematically reviews the applications of MOF-based materials in energy and catalysis and reviews the research progress of MOF materials for atmospheric water harvesting, seawater uranium extraction, and triboelectric nanogenerators. Finally, this review looks forward to the challenges and opportunities of controlling the synthesis of MOFs through low-cost, improved conductivity, high-temperature heat resistance, and integration with machine learning. This review provides useful references for promoting the application of MOFs-based materials in the aforementioned fields.

Innovative engine test bench set-up for testing of exhaust gas aftertreatment and detailed gas species analysis for CNG-SI-operation

For an efficient reduction of methane slip, a precise understanding of exhaust gas after treatment under real conditions is essential. Since it is not possible to produce catalytic converters in near-series geometry on a laboratory scale, it is necessary to resort to significantly smaller sample catalysts. Therefore, an engine test bench was designed to ensure real operating conditions for such samples with the help of space velocity and temperature control. A comparison between the actual and reference values of the space velocity results in a small deviation of 0.1% on average. Furthermore, the pressure conditions at the catalyst have been measured showing a propagation of pressure oscillations from the engine outlet which in combination with the space velocity regulation show that real conditions could be applied to the catalyst sample. Subsequently, the exhaust gas concentrations were monitored with a Fourier transform infrared spectrometer. The catalyst material used is PdO on Al2O3, common for methane oxidation. The measurements show that the CH4 conversion is higher under lean conditions, but is below complete conversion. In a final comparison between purely stoichiometric operation and dithering, the course of the CH4 conversion rate over the test period is examined more closely. In addition to sampling pre- and post-catalyst, the exhaust gas composition is measured spatially resolved within a catalyst channel using special measurement technology. In the temporal course of the CH4 emissions, a stabilizing effect due to the change of the operating mode can be seen, showing that dithering seems to prevent further deactivation.

A review on Fe2O3‐based catalysts for toluene oxidation: catalysts design and optimization with the formation of abundant oxygen vacancies

Volatile organic compounds (VOCs) are typical pollutants with hazards for humans and the environment, and can be efficiently mitigated by catalytic combustion. Fe2O3‐based catalysts are a promising choice due to their low cost and strong redox ability. Several attempts have been made to promote the catalytic performance of Fe2O3 at low temperatures. This review summarizes the research progress on Fe2O3‐based catalysts for the oxidation of toluene, one of the most common and harmful VOC. Firstly, the properties and catalytical performance for Fe2O3‐based catalysts were summarized, and the reaction mechanisms for toluene oxidation on the surface of Fe2O3 were detailed to comprehend the role of oxygen vacancy. Then, the modification for single Fe2O3 catalysts, including synthesis parameters, structure and morphology control, has been introduced to reveal the correlation between physicochemical properties of catalysts and their activity. In addition, composite Fe2O3 catalysts, which can promote catalytic performance significantly due to the synergetic effect between different components, were comprehended. Finally, waste‐derived Fe2O3 catalysts with sustainable merit as converting waste into worth have been discussed. Moreover, the advanced machine learning tools, which are helpful in accelerating catalyst design, configuration optimization and reactivity prediction, have been introduced as an emerging research opportunity for the future.

CeO2 Nanoislands Enhance the Activity and Stability of Pt Nanoparticles Supported on Fibrous Mesoporous SiO2 for Catalytic Combustion of Propane

CeO₂ Nanoislands Enhance the Activity and Stability of Pt Nanoparticles Supported on Fibrous Mesoporous SiO₂ for Catalytic Combustion of Propane

Experimental study of low-temperature combustion performance in hydrogen/air mixtures over Pt–Cu/HZSM-5/cordierite bimetallic catalysts

Catalytic combustion provides a feasible technology to effectively avoid NOx formation due to the high temperature in the process of hydrogen combustion. Recently, the development of efficient and affordable catalysts has attracted extensive attention as the cost of noble metals remained high. In this study, a list of cordierite monolithic catalysts with low noble metal loading are prepared by introducing the appropriate amount of transition metals (Mn, Cu, Fe, Co, and Ce), and their catalytic performance are further investigated. On this basis, the study on catalytic stability and kinetic is carried out, and the synergistic interaction between the bimetals is revealed with comprehensive characterization methods. The results show that Cu could promote the reaction rate of the Pt-based catalyst which show the best catalytic performance with the Cu loading of 1 g/L. The ignition temperature T10 is 58.5 °C, and the burnout temperature T100 is 100 °C, with activation energy as low as 44.00 kJ/mol. The enhancement of the catalytic performance is attributed to the interaction between the bimetallic elements. On the one hand, the valence state of Cu and Pt is changed, and on the other hand the dispersion of Pt get improved, which contributed to the catalytic reaction rate.

Methane Combustion Kinetics over Palladium-Based Catalysts: Review and Modelling Guidelines

Fugitive methane emissions account for a significant proportion of greenhouse gas emissions, and their elimination by catalytic combustion is a relatively easy way to reduce global warming. New and novel reactor designs are being considered for this purpose, but their correct and efficient design requires kinetic rate expressions. This paper provides a comprehensive review of the current state of the art regarding kinetic models for precious metal catalysts used for the catalytic combustion of lean methane mixtures. The primary emphasis is on relatively low-temperature operation at atmospheric pressure, conditions that are prevalent in the catalytic destruction of low concentrations of methane in emission streams. In addition to a comprehensive literature search, we illustrate a detailed example of the methodology required to determine an appropriate kinetic model and the constants therein. From the wide body of literature, it is seen that the development of a kinetic model is not necessarily a trivial matter, and it is difficult to generalize. The model, especially the dependence on the water concentration, is a function of not only the active ingredients but also the nature of the support. Kinetic modelling is performed for six catalysts, one commercial and five that were manufactured in our laboratory, for illustration purposes.

Operando investigation of catalytic trichloroethylene combustion over metal-doped CeO2 nanorods

The remediation of chlorinated volatile organic compounds is an intractable issue for it typically requires high temperatures and generates undesirable byproducts. This work utilized a series of representative transition metals (i.e., Cr, Cu, V) to modify the morphology, surface oxygen, and acidity of the CeO2 nanorods for trichloroethylene (TCE) treatment. A spectroscopic operando DRIFT − online GCMS reactor was introduced to examine the catalytic performance and elucidate the reaction pathway. Among them, Cr-CeO2 exhibited 50 % (T50) and 90 % (T90) TCE conversions with no byproduct at 171 °C and 241 °C, respectively. The performances of Cu-CeO2 (T90 = 391 °C), V-CeO2 (T90 = 423 °C) and CeO2 (T90 = 494 °C) were inferior to Cr-CeO2 (T90 = 241 °C), with obvious C2Cl4 generated in the TCE oxidation. It reveals that TCE adsorbed on Cr-CeO2 is dechlorinated on acidic sites and oxidized to carbonate/formate intermediates by the surface oxygen then facilely to generate carbon oxides, while TCE is adsorbed as chlorinated species (CH2ClCH2O−) on the other three catalysts which occupy the surface and require higher temperature to be oxidized. The abundant medium-strong acidic sites and surface oxygen species of Cr-CeO2 nanorods are responsible for the low-temperature activation via C-Cl cleavage on acidic sites and fast oxidation of hydrocarbon intermediates in the TCE oxidation, respectively.

Creating Atomically Iridium-Doped PdOx Nanoparticles for Efficient and Durable Methane Abatement.

The urgent environmental concern of methane abatement, attributed to its high global warming potential, necessitates the development of methane oxidation catalysts (MOC) with enhanced low-temperature activity and durability. Herein, an iridium-doped PdOx nanoparticle supported on silicalite-1 zeolite (PdIr/S-1) catalyst was synthesized and applied for methane catalytic combustion. Comprehensive characterizations confirmed the atomically dispersed nature of iridium on the surface of PdOx nanoparticles, creating an Ir4f-O-Pdcus microstructure. The atomically doped Ir transferred more electrons to adjacent oxygen atoms, modifying the electronic structure of PdOx and thus enhancing the redox ability of the PdIr/S-1 catalysts. This electronic modulation facilitated methane adsorption on the Pd site of Ir4f-O-Pdcus, reducing the energy barrier for C-H bond cleavage and thereby increasing the reaction rate for methane oxidation. Consequently, the optimized PdIr0.1/S-1 showed outstanding low-temperature activity for methane combustion (T50 = 276 °C) after aging and maintained long-term stability over 100 h under simulated exhaust conditions. Remarkably, the novel PdIr0.1/S-1 catalyst demonstrated significantly enhanced activity even after undergoing harsh hydrothermal aging at 750 °C for 16 h, significantly outperforming the conventional Pd/Al2O3 catalyst. This work provides valuable insights for designing efficient and durable MOC catalysts, addressing the critical issue of methane abatement.

New method for the preparation of hierarchical nanotube K0.3xMnxCe1-xOδ catalysts and their excellent catalytic performance for soot combustion

A series of nanofibrous K-Mn-Ce composite oxide catalysts were prepared via a centrifugal spinning method for the first time, and their physicochemical properties were studied. The prepared K0.3xMnxCe1-xOδ metal oxide catalyst, which is a composite of CeO2 and cryptopotassium manganese-type K2-xMn8O16, exhibits a hierarchical nanotube structure with uniform nanoneedles on its surface. During the process of soot oxidation, CeO2 utilizes its unique oxygen storage and release capacity to supply oxygen species. Simultaneously, the excellent redox properties of K2-xMn8O16 effectively promote valence cycling of the active components and produce more active oxygen species. This synergistic effect effectively enhances the intrinsic activity of the catalysts. Among the prepared catalysts, K0.15Mn0.5Ce0.5Oδ exhibits the highest catalytic performance, with 10% (T10), 50% (T50), and 90% (T90) soot conversion temperatures of 267 °C, 309 °C, and 338 °C, respectively, and shows good stability and water and sulfur resistance. Based on their simple preparation, low cost, and good catalytic performance, K0.3xMnxCe1-xOδ composite metal oxide catalysts have good potential in catalytic soot combustion applications.

Catalytic Conversion for Clean Energy: From Basics to Applications

Catalytic Conversion for Clean Energy: From Basics to Applications

Plasma driven exsolution of Ca as the adjacent dechlorinated site in La0.8Ca0.2MnO3 perovskite: A highly mineralization chlorobenzene oxidation catalyst

The degradation of chlorine-containing volatile organic compounds (CVOCs) catalytic combustion technology is subject to the catalyst chlorine poisoning, which is resulted from the chlorination of active phases, even though the structural stable perovskite. The reaction between Ca species and dissociated chlorine species is demonstrated as an efficient way to inhibited chlorine poisoning of the active phase. Herein, a Ca substituted partial La prepared La0.8Ca0.2MnO3 (named as L8C2MO) perovskite was treated by 5% H2/Ar plasma driven route (the treated sample was denoted as L8C2MO-P), which was applied for the chlorobenzene oxidation removal. The integrated characterization results of XRD, XPS, HRTEM, etc. confirmed that Ca (mainly exhibited as CaCO3) was successfully exsolved from La0.8Ca0.2MnO3 and simultaneously leaved oxygen vacancies on the surficial layers. The continuous catalytic oxidation experiments illustrated that the conversion efficiency of L8C2MO was unexpectedly decreased compared with that of LaMnO3 (LMO in short) sample, while that of L8C2MO-P was nearly maintained the oxidation capacity, with approximately 12 °C of 90% chlorobenzene conversion temperature (T90) higher than that of LMO. Importantly, the CO2 and inorganic chlorine species yields were significantly enhanced for L8C2MO and L8C2MO-P. The characteristic of used samples showed a possible chlorinated Ca species formation while the status of Mn phases was hardly changed, suggesting the exsolved Ca could inhibit the poison of Mn sites by binding with dissociative chlorine species. Additionally, oxygen vacancies that generated along with Ca exsolution process was definitely contributed to the deep oxidation of chlorobenzene. The possible reaction route was also studied by in situ DRIFTS and GCMS. The work provides a potential route as in situ growth of adjacent sites to protect active phases from chlorine poison in CVOCs catalytic oxidation process.