Synergy of heterogeneous Co/Ni dual atoms enabling selective C-O bond scission of lignin coupling with in-situ N-functionalization

Selective cleavage of Csp^(2)-OCH_(3)bond in lignin without breaking other types of C-O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass.Here,a Co/Ni-based dual-atom catalyst CoNiDA@NC prepared by in-situ evaporation and acid-etching of metal species from tailor-made metal–organic frameworks was efficient for reductive upgrading of various lignin-derived phenols to cyclohexanols(88.5%–99.9%yields),which had ca.4 times higher reaction rate than the single-atom catalyst and was superior to state-of-the-art heterogeneous catalysts.The synergistic catalysis of Co/Ni dual atoms facilitated both hydrogen dissociation and hydrogenolysis steps,and could optimize adsorption configuration of lignin-derived methoxylated phenols to further favor the Csp^(2)-OCH_(3)cleavage,as elaborated by theoretical calculations.Notably,the CoNi_(DA)@NC catalyst was highly recyclable,and exhibited excellent demethoxylation performance(77.1%yield)in real lignin monomer mixtures.Via in-situ cascade conversion processes assisted by dual-atom catalysis,various high-value N-containing chemicals,including caprolactams and cyclohexylamines,could be produced from lignin.

Heterogeneous catalysis under flow for the 21st century fine chemical industry

Due to metal leaching and poor catalyst stability, the chemical industry's fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine chemicals and active pharmaceutical ingredients. With the advent of new generation supported metal catalysts and flow chemistry, we argue in this study, this situation is poised to quickly change. Alongside heterogenized metal nanoparticles, both single-site molecular and single-atom catalyst will become ubiquitous. This study offers a critical outlook taking into account both technical and economic aspects.

Recent progress on synthesis of ZIF-67-based materials and their application to heterogeneous catalysis

In recent years,an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area,tunable porosity,and excellent thermal and chemical stabilities.This review summarizes the latest strategies of synthesizing ZIF-67-based materials by exploring the prominent examples.Then,the recent progress in the applications of ZIF-67-based materials in heterogeneous catalysis,including catalysis of the redox reactions,addition reactions,esterification reactions,Knoevenagel condensations,and hydrogenation-dehydrogenation reactions,has been elaborately discussed.Finally,we end this work by shedding some light on the large-scale industrial production of ZIF-67-based materials and their applications in the future.

Chlorobenzene degradation by electro-heterogeneous catalysis in aqueous solution:intermediates and reaction mechanism

This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentration on CB degradation were determined.The degradation effciency of CB was almost 100% with an initial CB concentration of 50 mg/L,current density 15 mA/cm2,initial pH 10,electrolyte concentration 0.1 mol/L,and temperature 25°C after 90 min of reaction.Under the same conditions,the degradation eff...

Progress on Porous Ceramic Membrane Reactors for Heterogeneous Catalysis over Ultrafine and Nano-sized Catalysts

Heterogeneous catalysts with ultrafine or nano particle size have currently attracted considerable attentions in the chemical and petrochemical production processes, but their large-scale applications remain challenging because of difficulties associated with their efficient separation from the reaction slurry. A porous ceramic membrane reactor has emerged as a promising method to solve the problem concerning catalysts separation in situ from the reaction mixture and make the production process continuous in heterogeneous catalysis. This article presents a review of the present progress on porous ceramic membrane reactors for heterogeneous catalysis, which covers classification of configurations of porous ceramic membrane reactor, major considerations and some important industrial applications. A special emphasis is paid to major considerations in term of application-oriented ceramic membrane design, optimization of ceramic membrane reactor performance and membrane fouling mechanism. Finally, brief concluding remarks on porous ceramic membrane reactors are given and possible future research interests are also outlined.

Study on the Mechanism of Heterogeneous Catalysis (4)—Electron Cyclic Donate-Accept Catalysis Mechanism-ECDAM or Electron Orbital Deformation-Reversion Cyclic Catalysis Mechanism-EODRM

This paper has expounded the derivation of the Electron Cyclic Donate-Accept Catalysis Mechanism-ECDAM or Electron Orbital Deformation-Reversion Cyclic Catalysis Mechanism-EODRM and its three main arguments as well as three argument verifications. These three main arguments are: 1) There is a demarcation between catalysts and poisons, or promoters and poisons. 2) The relative activities of catalysts or poisons of poisons are closely related to the Electrical Negativity Values-ENV of catalysts or poison. 3) The activities or ENVs of catalysts are closely related to the chemical states of substance being added. The ECDAM or EODRM can also be extended to iron or metal base catalyst for selecting promoter, support and judging poison. It can also be extended to the study of the fire retardant of carbon materials. The author holds that the catalytic phenomenon should be physical phenomenon rather than chemical phenomenon or not completely chemical phenomenon at least.

Study on the Mechanism of Heterogeneous Catalysis (1) —The Measurement of Equilibrium Pressure of Reaction BaCO₃+ C = BaO + 2CO, the Chemical States of Fe in Reaction Tank, and Chemical Reaction Model Catalytic Cycle Mechanism (CRMM)

The results on the equilibrium pressure measurement of BaCO3 + C = BaO + 2CO reaction and the demonstration of chemical state of iron proved that decomposition-generation cycle of BaCO3 and oxidation-reduction cycle of Fe in that reaction condition case were impossible to occur. The Chemical Reaction Model Catalytic Cycle Mechanism-CRMM does not exist at all for BaCO3, Fe, Noble metal catalysts. To call CRMM as a “principle” was obviously inappropriate. The TOF (Turnover Frequency—TOF: unit: s-1) was used to measure the activity size and life of catalyst, and it is clearly out of nothing.

TWO-STEP MECHANISM IN HETEROGENEOUS CATALYSIS AND DYNAMIC ANALYSIS

Recent development of the dynamic analysis technique has made it possible to measure separately kinetic parameters of a catalytic reaction as well as to study the effect of catalyst preparation parameters. But its application is still limned to first-order reaction. This work is aimed to demonstrate in some detail that,by comparison of the reaction rate expressions with the two-step mechanism used in catalytic kinetics and dynamic analysis, these methods can be extended to non-first-order reaction, and the kinetic parameters measured by dynamic techniques are interpreted for different reaction mechanisms.

Study on the Mechanism of Heterogeneous Catalysis (2) <br>—The Relative Catalytic Activities of Fe, Co, Ni, Cu, Ag and SiO2 in the Carbon Catalyzed Gasification Reaction

This is a validation article. The experimental results such as the relative catalytic activities of Fe, Co, Ni, Cu, Ag and SiO2 poisoning in the carbothermic reduction iron oxide show that the Electron Cyclic Donate-Accept Catalytic Mechanism-ECDAM or Electron Obital Deformation-Recovery cycle Catalysis Mechanism-EODRM are credible, and the Chemical Reaction Model Catalytic Cyclic Mechanism-CRMM such as the Oxygen Transfer Mechanism-OTT that is long and wide spread in the literature is completely unreliable. Because the Fe, Co, Ni, Cu, Ag were unlikely to react cyclic oxidation—reduction reaction with the carbon in the carbon reduction reaction tank.

Study on the Mechanism of Heterogeneous Catalysis (3) —The Catalysis of W, Mo, S and SiO₂on Carbon Dissolving and Mechanism of Carbon Dissolving in the Iron-Graphite Compact

This is an article that validates Electron Cyclic Donate-Accept Catalysis Mechanism-ECDAM or Electron Orbital Deformation-Recovery Cycle Catalysis Mechanism-EODRM. In this paper, the influence of compact density, sintering temperature and time, vacuum degree, atmosphere and alloying element on the carbon dissolving rate into γ-Fe were studied. The experiment results have been reported. The way that the carbon is dissolved into γ-Fe was discussed. Gas phase composition and temperature play an important role on the carbon dissolving rate. The carbon gasification reaction is the determining step of dissolving carbon process. K2CO3, W and Mo are a catalysts, and their active size are K2CO3 > W > Mo. S and SiO2 are a poison, and their poison size are SiO2 > S. The experiment results are completely consistent with the original judgment of ECDAM.

A Comparison of Two Heterogeneous Catalysis Mechanisms

In this paper, two heterogeneous catalysis mechanisms are introduced, namely: Chemical Reaction Mode Cyclic Catalysis Mechanism—CRMM and Electron Orbital Deformation-Recovery Cyclic Catalysis Mechanism—EODRM (or Electron Cyclic Donate-Adopt catalysis Mechanism—ECDAM. A number of difficulties encountered by CRMM are listed. The author clearly points out that CRMM is not credible. This false theory has misled us for more than 100 years. About EODRM or ECDAM, the article also gives a brief description. The key point of EODRM or ECDAM is that catalysts do not participate in chemical reactions, and catalysis phenomena are physical rather than chemical phenomena. It’s completely different from CRMM. The theory contains three main points: 1) There is a demarcation between the catalyst and the poison;2) The active size of the catalyst or the poison size of the poison is closely related to the electronegative size of the catalyst or poison;3) The active size of catalyst is closely related to the chemical state. The selectivity of catalyst is related to energy level. Photocatalysis, electrocatalysis, laser catalysis and microwave catalysis are all physical phenomena. It has different energy levels. According to this theory, the author thinks that there are several problems worth studying in production and scientific research, such as: alumina in the Fe ammonia synthesis catalyst has a serious poison effect on the iron catalyst, resulting in three high situations in ammonia synthesis production (high temperature, high pressure, high energy consumption). The support materials of automotive exhaust purification catalyst have used Cordierite (2MgO-2Al2O3-5SiO2) ceramic honeycomb support, which has a serious poisoning effect on noble metal catalysts, a lot of noble metals are wasted, and so on. These problems have long been ignored by the catalytic academia;the author considers that this reason may be due to a misunderstanding or mistranslation on the term “catalysis” and “catalyst”.

Surface reconstruction,modification and functionalization of natural diatomites for miniaturization of shaped heterogeneous catalysts

Since the discovery of mesoporous silica in 1990s,there have been numerous mesoporous silica-based nanomaterials developed for catalytic applications,aiming at enhanced catalytic activity and stability.Recently,there have also been considerable interests in endowing them with hierarchical porosities to overcome the diffusional limitation for those with long unimodal channels.Present processes of making mesoporous silica largely rely on chemical sources which are relatively expensive and impose environmental concerns on their processes.In this regard,it is desirable to develop hierarchical silica supports from natural minerals.Herein,we present a series of work on surface reconstruction,modification,and functionalization to produce diatomite-based catalysts with original morphology and macro-meso-micro porosities and to test their suitability as catalyst supports for both liquid-and gas-phase reactions.Two wet-chemical routes were developed to introduce mesoporosity to both amorphous and crystalline diatomites.Importantly,we have used computational modeling to affirm that the diatomite morphology can improve catalytic performance based on fluid dynamics simulations.Thus,one could obtain this type of catalysts from numerous natural diatoms that have inherently intricate morphologies and shapes in micrometer scale.In principle,such catalytic nanocomposites acting as miniaturized industrial catalysts could be employed in microfluidic reactors for process intensification.

Cooperative catalysis of Co single atoms and nanoparticles enables selective CAr-OCH_(3) cleavage for sustainable production of lignin-based cyclohexanols

In this work,a dual-size MOF-derived Co catalyst(0.2Co_(1-NPs)@NC)composed of single atoms(Co_(1))and highly dispersed nanoparticles(Co NPs)was prepared by in-situ Zn evaporation for the highperformance conversion of lignin-derived o-methoxyphenols(lignin oil)to cyclohexanols(up to 97%yield)via cascade demethoxylation and dearomatization.Theoretical calculations elaborated that the dual-size Co catalyst exhibited a cooperative effect in the selective demethoxylation process,in which the Co NPs could initially dissociate hydrogen at lower energies while Co1remarkably facilitated the cleavage of the C_(Ar)-OCH_(3)bond.Moreover,the intramolecular hydrogen bonds formed in the omethoxy-containing phenols were found to result in a decrease in the bond energy of the C_(Ar)-OCH_(3)bond,which was more prone to be activated by the dual-size Co sites.Notably,the pre-hydrogenated intermediate(e.g.,2-methoxycyclohexanol from guaiacol)is difficult to undergo demethoxylation,indicating that the selective C_(Ar)-OCH_(3)bond cleavage is a prerequisite for the synthesis of cyclohexanols.The 0.2Co_(1-NPs)@NC catalyst was highly recyclable with a neglect decline in activity during five consecutive cycles.This cooperative catalytic strategy based on the metal size effect opens new avenues for biomass upgrading via enhanced C-O bond cleavage of high selectivity.

Kinetics of the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation

In this study,high-gravity intensified heterogeneous catalytic ozonation is utilized for treatment of phenol-containing wastewater,and the kinetics of the direct reaction between ozone and phenol in the presence of excess tertiary butanol(TBA)is investigated.It is revealed that the direct reaction between ozone and phenol in the rotating packed bed(RPB)follows the pseudo-first-order kinetics with a reaction rate constant higher than that in the conventional bubbling reactor(BR).Under different conditions of temperature,initial pH,high-gravity factor,and gaseous ozone concentration,the apparent reaction rate constant varies in the range of 0.0160–0.115 min-1.An empirical power-exponential model is established to characterize the effects of these parameters on the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation.

Efficient homogenous catalysis of CO_(2) to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

The cycloaddition between CO_(2)and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO_(2)as C1 source.The development of catalyst to mediate cycloaddition between CO_(2)and epoxides at low temperature and pressure is still a challenge.Herein,a series of polypyrazoles with glass transition temperature(T_(g))in the range of 42.3-52.5℃ were synthesized and served as catalyst to mediate the cycloaddition of CO_(2)and epoxides by the assistant of tetrabutylammonium bromide.The catalytic behaviors of polypyrazole on the model cycloaddition of CO_(2)to epichlorohydrin,including the reaction parameters optimization and versatility were investigated in detail,and excellent yield(99.9%)and selectivity(99%)were obtained under the optimized reaction conditions of70℃ and 1.0 MPa for 6.0 h.Noteworthily,the polypyrazole acts as homogeneous catalyst during reaction(higher than T_(g)).And under room temperature,polypyrazoles can be easily separated and recovered,which is a promising feature of a heterogeneous catalyst.Furthermore,the reaction mechanism was proposed.The DFT calculation suggested that the formation of hydrogen bond between pyrazole and epoxide greatly reduced the energy barrier,which play an important role in promoting CO_(2)cycloaddition.

REACTION OF ETHYL N-CYANOMETHYLBENZEHECARBOXIMIDATE WITH ALIPHATIC ALDEHYDES UNDER THE SOLID-LIQUID PHASE TRANSFER CATALYSIS

Ethyl N-cyanomethytbenzenecarboximidate reacted with aliphatic aldehydes under the solid-liquid PTC condition to gire a-ethoxyphenylmethylene- aminoacrylonitrile derivatives and oxazoline derivatives.It is a convenient and new method for synthesis of β,β'-dihyroxy-a-amino acids by hydrolysis of the oxazoline derivatives.

Application of Heterogenous Catalysis with TiO2 Photo Irradiated by Sunlight and Latter Activated Sludge System for the Reduction of Vinasse Organic Load

Vinasse is the main residue generated during alcohol, sugar and blue rum production by fermentation process. This residue is effluent that could cause serious environmental pollution due to high organic load when is not treated adequately. The aim of this work consists of evaluating the efficiency and application of heterogeneous photocatalysis with TiO2, followed by a biological treatment (activated sludge system) to reduce organic load in the referred effluent. Complete factorial designs indicated the best experimental conditions subsequent to photacatalytic and biological treatments providing a reduction of non-purgeable organic carbon (NPOC) as a variable response. After the photocatalytic process, the sample from the best experiment condition was treated by a biological process in order to verify the degradation efficiency of the effluent organic matter studied according to the hybrid system (Advanced Oxidation Process—Acti- vated Sludge System). This system, which presented more efficiency, had a photochemical treatment of 180 minutes carried out in aerated solutions, pH 9 and effluent in natura, while the biological treatment was performed at pH 8 and sludge concentration of 5 gL–1. The reduction of biochemical oxygen demand (BOD) was >80%.

Heterogeneous activation of persulfate by CuMgAl layered double oxide for catalytic degradation of sulfameter

In this study,a series of CuMgAl layered double oxides(CuMgAl-LDOs)were obtained via calcination of CuMgAl layered double hydroxides(CuMgAl-LDHs)synthesised via a co-precipitation method.The results show that CuMgAl-LDO can be prepared using an optimal Cu:Mg:Al molar ratio of 3:3:2,NaOH:Na_(2)CO_(3)molar ratio of 2:1,and calcination temperature of 600°C.CuMgAl-LDO is a characteristic of mesoporous material with a lamellar structure and large specific surface area.The removal efficiency of sulfameter(SMD)based on CuMgAl-LDO/persulfate(PS)can reach>98%over a wide range of initial SMD concentrations(5–20 mg L^(-1)).The best removal efficiency of99.49%was achieved within 120 min using 10 mg L^(-1)SMD,0.3 g L^(-1)CuMgAl-LDO,and 0.7 mmol L^(-1)PS.Kinetic analysis showed that the degradation of SMD was in accordance with a quasi-first-order kinetic model.The stability of the CuMgAl-LDO catalyst was verified by the high SMD removal efficiency(>97%within 120 min)observed after five recycling tests and low copper ion leaching concentration(0.89 mg L^(-1)),which is below drinking water quality standard of 1.3 mg L^(-1)permittable in the U.S.Radical scavenging experiments suggest that SO_(4)^(-)is the primary active species participating in the CuMgAl-LDO/PS system.Moreover,our mechanistic investigations based on the radical scavenging tests and X-ray photoelectron spectroscopy(XPS)results indicate that Cu^((II))-Cu^((III))-Cu^((II))circulation is responsible for activating PS in the degradation of SMD and the degradation pathway for SMD was deduced.Accordingly,the results presented in this work demonstrate that CuMgAl-LDO may be an efficient and stable catalyst for the activation of PS during the degradation of organic pollutants.

Covalently anchored sulfonic acid on silica gel(SiO_2-R-SO_3H)as an efficient and reusable heterogeneous catalyst for the one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions

A highly efficient one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions catalyzed by sulfonic acid covalently anchored onto the surface of silica gel is reported. All types of aldehydes, including aromatic, unsaturated, and heterocyclic, are used. The silica gel/sulfonic acid catalyst （SiO2-R-SO3H） is completely heterogeneous and can be recycled.