Enhancing polyol/sugar cascade oxidation to formic acid with defect rich MnO2 catalysts.

Oxidation of renewable polyol/sugar into formic acid using molecular O2 over heterogeneous catalysts is still challenging due to the insufficient activation of both O2 and organic substrates on coordination-saturated metal oxides. In this study, we develop a defective MnO2 catalyst through a coordination number reduction strategy to enhance the aerobic oxidation of various polyols/sugars to formic acid. Compared to common MnO2, the tri-coordinated Mn in the defective MnO2 catalyst displays the electronic reconstruction of surface oxygen charge state and rich surface oxygen vacancies. These oxygen vacancies create more Mnδ+ Lewis acid site together with nearby oxygen as Lewis base sites. This combined structure behaves much like Frustrated Lewis pairs, serving to facilitate the activation of O2, as well as C-C and C-H bonds. As a result, the defective MnO2 catalyst shows high catalytic activity (turnover frequency: 113.5 h-1) and formic acid yield (>80%) comparable to noble metal catalysts for glycerol oxidation. The catalytic system is further extended to the oxidation of other polyols/sugars to formic acid with excellent catalytic performance.

Process Optimization of Para-xylene Crystallization Separation Process via Morphology Approach, Multi-dimensional Population Balance Equation, and Equation-Oriented Models.

An activity coefficient-based model was proposed to predict pertinent saturated concentrations in organic solid-liquid equilibrium, and the binary parameters of xylene mixtures were experimentally obtained. Also, a novel monocular 3D reconstruction technique was developed to measure crystal size and applied to derive the kinetics of nucleation and growth of para-xylene crystals. Subsequently, a multi-dimensional population balance equation was used to predict the particle size distribution in the crystallizer and an algorithm was designed to simulate and optimize the economic benefit of the crystallization separation process. Consequently, it became possible to predict the optimal coolant flowrate and inlet temperature, as well as the feed flowrate for a crystallization process with given operating conditions and device parameters.

Effect of Temperature on Asphaltene Precipitation in Crude Oils from Xinjiang Oilfield.

During the production of crude oil, asphaltenes are prone to precipitate due to the changes of external conditions (temperature, pressure, etc.). Therefore, a series of research studies were designed to investigate the effect of temperature on asphaltene precipitation for two Xinjiang crude oils (S1, S2) so as to reveal the mechanism of asphaltene dissolution. First, the changes of asphaltene precipitation were intuitively observed by using a microscope. The results demonstrated that the asphaltene solubility increased with the increase of temperature and the dispersion rate of asphaltene particles increased with the decrease of particle size. Second, the variation of asphaltene precipitation with temperature was quantified by a gravimetric method. The results suggested that the different asphaltenes showed different sensitivity to temperature within the temperature range 25-120 °C. Third, a hypothesis was proposed to explain these results and proved that the asphaltene aggregate structure was an important factor for asphaltene stability. The crystallite parameters of asphaltenes were obtained by X-ray diffraction (XRD) to describe the structural characteristics. The results revealed that the layer distance between aromatic sheets (d m ) of asphaltenes derived from S1 oil and S2 oil were 0.378 and 0.408 nm, respectively, which implied that the asphaltene aggregates derived from S2 oil were looser than those of S1 oil. Therefore, high temperature could facilitate the penetration of resins into asphaltene aggregates and ultimately improve the dispersion of asphaltenes. Finally, molecular dynamics (MD) simulation was used to verify the conclusions. Based on the molecular dynamics method, asphaltene aggregate models were developed. The compactness and internal energy of each model were calculated. The results showed that the asphaltene dispersion capability was proportional to the porosity and internal energy.

Atomically Dispersed CoN3 C1 -TeN1 C3 Diatomic Sites Anchored in N-Doped Carbon as Efficient Bifunctional Catalyst for Synergistic Electrocatalytic Hydrogen Evolution and Oxygen Reduction.

A encapsulation-adsorption-pyrolysis strategy for the construction of atomically dispersed Co-Te diatomic sites (DASs) that are anchored in N-doped carbon is reported as an efficient bifunctional catalyst for electrocatalytic hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). The as-constructed catalyst shows the stable CoN3 C1 -TeN1 C3 coordination structure before and after HER and ORR. The *OOH/*H intermediate species are captured by in situ Raman and in situ attenuated total reflectance-surface enhanced infrared absorption spectroscopy, indicating that the reactant O2 /H2 O molecule has a strong interaction with the Co site, revealing that Coδ+ is an effective active site. Theoretical calculations show that the Coδ+ has adsorption-activation function and the neighboring Teδ+ acts as an electron donor adjusting the electronic structure of Coδ+ , promoting the dissociation of H2 O molecules and the adsorption of H and oxygen-containing intermediates in HER and ORR. In the meanwhile, the nearest C atom around Co also profoundly affects the adsorption of H atoms. This results in the weakening of the OH adsorption and enhancement of H adsorption, as well as the more stable water molecule dissociation transition state, thus significantly boosting ORR and HER performance.

Recent Advances on Synthesis of CoCO3 with Controlled Morphologies.

Cobalt carbonates and derivatives represent most promising cost-effective materials for energy storage, conversion and upgrading. Morphology determines the performances, as size, shape and electronic configuration are key factors for tunable properties in the area of batteries, catalysis, magnetics and plasmonics. However, there is lack of insights in literature on morphological control of cobalt carbonates during hydrothermal and solvothermal conditions. Therefore, this review provides detailed discussion on synthesis, formation mechanism and morphological control of nanosheets, wires, spheres and cubes of cobalt carbonates. Furthermore, the influence of experimental conditions and plausible mechanism which govern the growing processes were further discussed in details. The outcome of this short review will offer insights into rational design of inexpensive metal carbonates for numerous other energy and environment applications.

Synergistic advanced oxidation process for enhanced degradation of organic pollutants in spent sulfuric acid over recoverable apricot shell-derived biochar catalyst.

The sulfuric acid-based alkylation process, which leads the industrial application market, still struggles with effectively removing a large number of organic pollutants from hazardous spent sulfuric acid. A synergistic advanced oxidation process was constructed to degrade the organic pollutants with H2O2 and sodium persulfate as the synergistic oxidants and apricot shell-derived biochar (OBC) as the catalyst. Taking the total organic carbon (TOC) and the color scale as the indices, the effects of critical experimental factors, i.e., reaction temperature, initial oxidant concentration, catalyst dosage, and aeration rate, were optimized. The results showed that the removal rates of TOC and the color of the spent sulfuric acid reached ∼91% and 96.6%, respectively, after 150 min under the optimum conditions. Besides, the efficient and low-cost OBC catalyst developed in this study could be continuously used for at least four times with about 75% TOC removal and 80% color removal, exhibiting favorable stability and good resistance to acid corrosion. Further study confirmed that the SO4-˙ and ˙OH radicals generated in the synergistic advanced oxidation process strengthened the degradation and elimination of organic pollutants. The synergistic advanced oxidation process could provide a feasible insight for spent sulfuric acid treatment.

PO4 3- Coordinated Robust Single-Atom Platinum Catalyst for Selective Polyol Oxidation.

Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single-atom Pt1 /hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1 /HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2 -C4 polyols to corresponding primary hydroxy acids. It is found that the Pt-(O-P) linkages with strong electron-withdrawing function of PO4 3- (Pt1 -OPO4 3- pair active site) not only realize the activation of the C-H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C-C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO4 3- -coordination effect provides electrostatic stabilization for single-atom Pt, ensuring the highly efficient catalysis of Pt1 /HAP for over 160 hours with superior leaching resistance.

Mesoporogen-Free Strategy to Construct Hierarchical TS-1 in a Highly Concentrated System for Gas-Phase Propene Epoxidation with H2 and O2.

Hierarchical TS-1 has attracted enormous attention from both academia and industry due to its remarkable catalytic performance in epoxidation reactions. However, sustainable synthesis of hierarchical-nanosized TS-1 without mesoporogens is still challenging. In this work, we report a facile and mesoporogen-free strategy to simultaneously manipulate pore structure and particle size of TS-1 employing the concentrated system. Taking advantage of the suspended nuclei in the concentrated system as confirmed by the DLS-PSD and atomic force microscopy, the novel TS-1 is demonstrated to have higher Ti concentration on surface, higher surface area (539 m2/g), abundant mesopores, and reduced crystal size (ca. 150 nm). Moreover, this Au-Ti bifunctional catalyst shows a good PO formation rate with enhanced catalytic stability due to the hierarchical structure. This strategy opens a novel way for the green synthesis of hierarchical-nanosized TS-1 and facilitates industrial development of the Au/TS-1 catalyst for propene epoxidation.

Catalytic Transfer Hydrogenolysis of Glycerol over Heterogeneous Catalysts: A Short Review on Mechanistic Studies.

Catalytic transfer hydrogenolysis, using liquid H-donors in the absence of pressurized H2 under mild temperatures, is regarded as the most important technology to substitute traditional hydrogenation processes in industry. Despite decade development with several breakthroughs in catalyst design, the reaction mechanism involved in H2 generation and subsequent hydrogenolysis reactions is still under debate. In this review, transfer hydrogenolysis of glycerol, as a representative example, on metallic catalysts is revised critically with respect to surface reaction mechanism and catalyst design. The detailed reaction pathways for propanol, methanol, formic acid and ethanol for H2 generation have been discussed systematically. In particular, reaction mechanism for catalytic C-H cleavage, H spillover/transfer and C-O cleavage reaction steps will be critically revised with experimental and theoretical results in literature. Insights into reaction pathways, mechanism and H2 transfer efficiency and structure-performance relation for Pd, Cu and Ni catalysts will be provided for future development of catalyst manufacture and process development. The outcome of this work is useful for successful implementation of bio-refinery.

Regulating light olefins or aromatics production in ex-situ catalytic pyrolysis of biomass by engineering the structure of tin modified ZSM-5 catalyst.

Valorization of biomass to olefin or aromatics harbours tremendous practical value due to growing concerns about sustainable production of chemicals. Herein, the olefin or aromatics yields of ex-situ catalytic pyrolysis of pine can be regulated by impregnating Sn on hollow-structured ZSM-5 (M-ZSM-5) and microporous ZSM-5 catalysts in fixed-bed reactor, respectively. Results showed that Sn/ZSM-5 catalyst simultaneously increased medium acidic sites and maintained strong acidic sites, which obtained the maximum carbon yield of aromatics (33.77%) due to enhanced cracking and deoxygenation reactions. In addition, Sn boosted alkylation between olefin and aromatics, generating more alkylbenzene. In contrast, Sn/M-ZSM-5 catalyst produced the highest olefins carbon yield (12.39%) because the reduction of strong acidic sites and microporous volume inhibited the olefin aromatization. Moreover, olefins were easier to desorb from Sn/M-ZSM-5 due to the enhanced mass transfer ability, which weakened the alkylation reactions. The synergistic effect harbours great significance to manipulate the distribution of products.

Hydrogenolysis of Glycerol to Propylene Glycol: Energy, Tech-Economic, and Environmental Studies.

Hydrogenolysis of glycerol to propylene glycol represents one of the most promising technologies for biomass conversion to chemicals. However, conventional hydrogenolysis processes are often carried out under harsh H2 pressures and temperatures, leading to intensive energy demands, fast catalyst deactivation, and potential safety risks during H2 handling. Catalytic transfer hydrogenolysis (CTH) displays high energy and atom efficiency. We have studied a series novel solid catalysts for CTH of glycerol. In this work, detailed studies have been conducted on energy optimization, tech-economic analysis, and environmental impact for both processes. The key finding is that relatively less energy demands and capital investment are required for CTH process. CO2 emission per production of propylene glycol is much lower in the case of transfer hydrogenolysis. The outcome of this study could provide useful information for process design and implementation of novel hydrogenolysis technologies for other energy and environmental applications.

Reversing Titanium Oligomer Formation towards High-Efficiency and Green Synthesis of Titanium-Containing Molecular Sieves.

Green and efficient synthesis of titanium-containing molecular sieves is limited by the quantity of environmentally unfriendly additives and complicated synthesis procedures required. Oligomerization of Ti monomers into anatase TiO2 is the typical outcome of such procedures because of a mismatch between hydrolysis rates of Si and Ti precursors. We report a simple and generic additive-free route for the synthesis of Ti-containing molecular sieves (MFI, MEL, and BEA). This approach successfully reverses the formation of Ti oligomers to match hydrolysis rates of Ti and Si species with the assistance of hydroxyl free radicals generated in situ from ultraviolet irradiation. Moreover, fantastic catalytic performance for propene epoxidation with H2 and O2 was observed. Compared with the conventional hydrothermal method, this approach opens up new opportunities for high-efficiency, environmentally benign, and facile production of pure titanium-containing molecular sieves.

Catalytic Deoxygenation of Xylitol to Renewable Chemicals: Advances on Catalyst Design and Mechanistic Studies.

Xylitol is commonly known as one of the top platform intermediates for biomass conversion. Catalytic deoxygenation of xylitol provides an atomic and energetic efficient way to produce a variety of renewable chemicals including ethylene glycol, 1,2-propanediol, lactic acid and 1,4-anhydroxylitol. Despite a few initial attempts in converting xylitol into those products, improving catalyst selectivity towards C-O and C-C cleavage reactions remains a grand challenge in this area. To our best knowledge, there is lack of comprehensive review to summarize the most recent advances on catalyst design and mechanisms in deoxygenation of xylitol, offering important perspective into future development of xylitol transformation technologies. Therefore, in this mini-review, we have critically discussed the conversion routes involved in xylitol deoxygenation over solid catalyst materials, the nanostructures of supported metal catalysts for C-H, C-C and C-O bond cleavage reactions, and mechanistic investigation for xylitol conversion. The outcome of this work provides new insights into rational design of effective deoxygenation catalyst materials for upgrading of xylitol and future process development in converting hemicellulosic biomass.

Effect of Phosphorus Modification on the Acidity, Nanostructure of the Active Phase, and Catalytic Performance of Residue Hydrodenitrogenation Catalysts.

A series of NiMoP(x)-Al catalysts with different phosphorus contents were prepared by the incipient wetness co-impregnation method. The effects of phosphorus modification on the acidity, active phase nanostructure, and catalytic properties of the residue hydrodenitrogenation catalysts were investigated to find the role of phosphorus in the catalytic mechanism. The results of temperature-programmed desorption of NH3 and pyridine IR spectroscopy of the catalysts indicate that phosphorus modification can increase the total acid and Brønsted acid. Transmission electron microscopy analysis shows that phosphorus modification increases the stacking number N A, reduces the slab length L A of the active MoS2 phase, and increases the Mo dispersion f Mo, leading to the promotion of the sulfidation degree of the active Mo phase and thus increasing the denitrification rate. The catalyst with a 3.4 wt % P2O5 loading shows the highest Brønsted/Lewis acid ratio, the largest amount of three-layer active phases, the smallest L A, the highest f Mo, the optimal sulfurization degree, and the highest denitrification rate, 63.6%, indicating the correlation between the nanostructure of the active phase and its catalytic property because of the addition of phosphorus.

Recent Advances on Purification of Lactic Acid.

With increasing interest in developing biodegradable polymers to replace fossil-based products globally, lactic acid (LA) has been paid extensive attention due to the high environment-compatibility of its downstream products. The mainstream efforts have been put in developing energy-efficient conversion technologies through biological and chemical routes to synthesize LA. However, to our best knowledge, there is a lack of sufficient attention in developing effective separation technologies with high atom economics for purifying LA and derivatives. In this review, the most recent advances in purifying LA using precipitation, reactive extraction, emulsion liquid membrane, reactive distillation, molecular distillation, and membrane techniques will be discussed critically with respect to the fundamentals, flow scheme, energy efficiency, and equipment. The outcome of this article is to offer insights into implementing more atomic and energy-efficient technologies for upgrading LA.

Investigation on Adsorption and Separation Behavior of Propane/Propene Mixtures in Zeolites.

Propane/propene separation is among the most energy-intensive separation processes in the petrochemical industry. Separation based on adsorption on a nanoporous material (e.g., zeolites) has spawned new ideas for this process. Therefore, we conducted grand canonical ensemble Monte Carlo simulations to investigate the adsorption and separation of propane and propene in one-dimensional (ATS, MOR, and AWO), two-dimensional (MWW, FER, and BOG) and three-dimensional (MFI, BEA, FAU) zeolites. The computation of pure components indicates that the adsorption capacity is affected by the zeolite pore diameter, dimensionality, and isosteric heat. For a given diameter, three dimensional zeolites exhibit better adsorption properties than two or one-dimensional zeolites. Zeolites with diameters ranging from 4.8 Å to 5.4 Å show high propane and propene affinity. In binary mixture simulations, the separation capacity of propane and propene increases with elevated pressure and decreased temperature. Among these zeolites, AWO exhibits the best separation performance due to its eight-ring window channel, which is consistent with experimental results. Thus, our results provide better understanding on propane and propene adsorption and separation in different zeolites, as well as insight into how production conditions could be upgraded.

Catalytic Transfer Hydrogenation of Biomass-Derived Substrates to Value-Added Chemicals on Dual-Function Catalysts: Opportunities and Challenges.

Aqueous-phase hydrodeoxygenation (APH) of bioderived feedstocks into useful chemical building blocks is one the most important processes for biomass conversion. However, several technological challenges, such as elevated reaction temperature (220-280 °C), high H2 pressure (4-10 MPa), uncontrollable side reactions, and intensive capital investment, have resulted in a bottleneck for the further development of existing APH processes. Catalytic transfer hydrogenation (CTH) under much milder conditions with non-fossil-based H2 has attracted extensive interest as a result of several advantageous features, including high atom efficiency (≈100 %), low energy intensity, and green H2 obtained from renewable sources. Typically, CTH can be categorized as internal H2 transfer (sacrificing small amounts of feedstocks for H2 generation) and external H2 transfer from H2 donors (e.g., alcohols, formic acid). Although the last decade has witnessed a few successful applications of conventional APH technologies, CTH is still relatively new for biomass conversion. Very limited attempts have been made in both academia and industry. Understanding the fundamentals for precise control of catalyst structures is key for tunable dual functionality to combine simultaneous H2 generation and hydrogenation. Therefore, this Review focuses on the rational design of dual-functionalized catalysts for synchronous H2 generation and hydrogenation of bio-feedstocks into value-added chemicals through CTH technologies. Most recent studies, published from 2015 to 2018, on the transformation of selected model compounds, including glycerol, xylitol, sorbitol, levulinic acid, hydroxymethylfurfural, furfural, cresol, phenol, and guaiacol, are critically reviewed herein. The relationship between the nanostructures of heterogeneous catalysts and the catalytic activity and selectivity for C-O, C-H, C-C, and O-H bond cleavage are discussed to provide insights into future designs for the atom-economical conversion of biomass into fuels and chemicals.

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals.

Conversion of biomass to chemicals provides essential products to human society from renewable resources. In this context, achieving atom-economical and energy-efficient conversion with high selectivity towards target products remains a key challenge. Recent developments in nanostructured catalysts address this challenge reporting remarkable performances in shape and morphology dependent catalysis by metals on nano scale in energy and environmental applications. In this review, most recent advances in synthesis of heterogeneous nanomaterials, surface characterization and catalytic performances for hydrogenation and oxidation for biorenewables with plausible mechanism have been discussed. The perspectives obtained from this review paper will provide insights into rational design of active, selective and stable catalytic materials for sustainable production of value-added chemicals from biomass resources.

Adsorption and separation of n/iso-pentane on zeolites: A GCMC study.

Separation of branched chain hydrocarbons and straight chain hydrocarbons is very important in the isomerization process. Grand canonical ensemble Monte Carlo simulations were used to investigate the adsorption and separation of iso-pentane and n-pentane in four types of zeolites: MWW, BOG, MFI, and LTA. The computation of the pure components indicates that the adsorption capacity is affected by physical properties of zeolite, like pore size and structures, and isosteric heat. In BOG, MFI and LTA, the amount of adsorption of n-pentane is higher than iso-pentane, while the phenomenon is contrary in MWW. For a given zeolite, a stronger adsorption heat corresponds to a higher loading. In the binary mixture simulations, the separation capacity of n-and iso-pentane increases with the elevated pressure and the increasing iso-pentane composition. The adsorption mechanism and competition process have been examined. Preferential adsorption contributions prevail at low pressure, however, the size effect becomes important with the increasing pressure, and the relatively smaller n-pentane gradually competes successfully in binary adsorption. Among these zeolites, MFI has the best separation performance due to its high shape selectivity. This work helps to better understand the adsorption and separation performance of n- and iso-pentane in different zeolites and explain the relationship between zeolite structures and adsorption performance.