Enhanced recycling performance of bimetallic Ir-Re/SiO_(2) catalyst by amberlyst-15 for glycerol hydrogenolysis

Recycling performance of heterogeneous catalysts is of crucial importance especially for a batch reaction system.In this work,we demonstrate a strategy for enhancing recycling performance of Ir-Re/SiO_(2) catalyst synergized with amberlyst-15 in glycerol hydrogenolysis to produce 1,3-propanediol.Comprehensive characterization results reveal that the Re sites in the Ir-Re/SiO_(2) catalyst undergo irreversible segregation and oxidation.These hinder the formation of active ReAOH species and thus contribute to a complete and irreversible deactivation.However,the introduction of amberlyst-15 into the reactant mixture can restrain the oxidation process of Re sites and favor the formation of ReAOH species,and thus significantly enhance the catalytic recycling performance.The results demonstrated here could guide the development of excellent bimetallic catalysts with the desirable recycling performances for the reaction.

General trends in Horiuti-Polanyi mechanism vs non-Horiuti-Polanyi mechanism for water formation on transition metal surfaces

It is generally acknowledged in heterogeneous catalysis that hydrogenation follows the so-called Horiuti-Polanyi(HP) mechanism. In this work, a thorough investigation of the mechanism of hydrogenation of hydroxyl groups and O catalyzed by a series of transition metals was carried out through density functional theory calculations, as surface hydroxyls and O are very common species in many catalytic systems. It is found that different metal catalysts exhibit different mechanisms. On some metal catalysts, the non-HP mechanism is preferred, whereas the classic HP mechanism is favored on other catalysts. Detailed analyses of the metal-dependent mechanism shows that the activity toward the dissociation of H2 decides which mechanism is preferred. On active catalysts, such as Ni and Pt, H2 prefers to dissociate with strong H adsorption energies, which lead to the classic HP mechanism being favored. On inactive surfaces, on the other hand, the adsorption of H is weak, which results in the non-HP mechanism being preferred. The parameter η, which is a structural descriptor, was defined to understand the different mechanisms.

A density functional theory study of polarons on different TiO_(2) surfaces

Polarons are widely considered to play a crucial role in the charge transport and photocatalytic performance of materials,but the mechanisms of their formation and the underlying driving factors remain a matter of controversy.This study delves into the formation of polarons in different crystalline forms of TiO_(2) and their connection with the materials'structure.By employing density functional theory calculations with on-site Coulomb interaction correction(DFT+U),we provide a detailed analysis of the electronic polarization behavior in the anatase and rutile forms of TiO_(2).We focus on the polarization properties of defect-induced and photoexcited excess electrons on various TiO_(2) surfaces.The results reveal that the defect electrons can form small polarons on the anatase TiO_(2)(101)surface,while on the rutile TiO_(2)(110)surface,both small and large polarons(hybrid-state polarons)are formed.Photoexcited electrons are capable of forming both small and large polarons on the surfaces of both crystal types.The analysis indicates that the differences in polaron distribution are primarily determined by the intrinsic properties of the crystals;the structural and symmetry differences between anatase and rutile TiO_(2) lead to the distinct polaron behaviors.Further investigation suggests that the polarization behavior of defect electrons is also related to the arrangement of electron orbitals around the Ti atoms,while the polarization of photoexcited electrons is mainly facilitated by the lattice distortions.These findings elucidate the formation mechanisms of different types of polarons and may contribute to understanding the performance of TiO_(2)in different fields.

Activity and selectivity of propane oxidative dehydrogenation over VO_3/CeO_2(111) catalysts: A density functional theory study

The oxidative dehydrogenation（ODH） of propane on monomeric VO3 supported by CeO2（111）（VO3/CeO 2（111）） is studied by periodic density functional theory calculations. Detailed energetic, structural, and electronic properties of these reactions are determined. The calculated activation energies of the breaking of the first and second C–H bonds of propane on the VO3/CeO2（111） catalyst are compared, and it is found that both the unique structural and electronic effects of the VO3/CeO2（111） catalyst contribute to the relatively easy rupture of the first C–H bond of the propane molecule during the ODH reaction. In particular, the so-called new empty localized states that are mainly constituted of O2 porbitals of the ceria-supported VO3 species are determined to be crucial for assisting the cleavage of the first C–H bond of the propane molecule. Following this they become occupied and the remaining C–H bonds become increasingly difficult to break owing to the increasing repulsion between the localized 4 felectrons at the Cecations, resulting in the adsorption of more H and other moieties. This work illustrates that CeO2-supported monomeric vanadium oxides can exhibit unique activity and selectivity for the catalytic ODH of alkanes to alkenes.

CuSx-mediated two reaction systems enable biomimetic photocatalysis in CO_(2) reduction with visible light

The performances of heterogeneous catalysts can be effectively improved by optimizing the catalysts via appropriate structure design.Herein,we show that the catalysis of cuprous sulfide can be boosted by constructing the hybrid structure with Cu_(2)S nanoparticles on amorphous CuSx matrix(Cu_(2)S/CuSx).In the photocatalytic CO_(2) reduction under visible light irradiation,the Cu_(2)S/CuSx exhibited a CO production rate at 4.0μmol h-1 that is 12-fold higher than that of the general Cu_(2)S catalyst.Further characterizations reveal that the Cu_(2)S/CuSx has two reaction systems that realize the biomimetic catalysis,involving in the light reaction on the Cu_(2)S nanoparticle-CuSx matrix heterojunctions for proton/electron production,and the dark reaction on the defect-rich CuSx for CO_(2) reduction.The CuSx matrix could efficiently activate CO_(2) and stabilize the split hydrogen species to hinder undesired hydrogen evolution reaction,which benefits the proton-electron transfer to reduce CO_(2),a key step for bridging the two reaction systems.

Substituent Effects on the Photocatalytic Properties of a Symmetric Covalent Organic Framework

Symmetric covalent organic framework(COF)photocatalysts generally suffer from inefficient charge separation and short-lived photoexcited states.By performing density functional theory(DFT)and time-dependent density functional theory(TDDFT)calculations,we find that partial substitution with one or two substituents(N or NH_(2))in the linkage of the representative symmetric COF(N_(0)-COF)gives rise to the separation of charge carriers in the resulting COFs(i.e.,N_(1)-COF,N_(2)-COF,(NH_(2))1-N_(0)-COF,and(NH_(2))2-N_(0)-COF).Moreover,we also find that the energy levels of the highest occupied crystal orbital(HOCO)and the lowest unoccupied crystal orbital(LUCO)of the N_(0)-COF can shift away from or toward the vacuum level,depending on the electron-withdrawing or electron-donating characters of the substituent.Therefore,we propose that partial substitution with carefully chosen electron-withdrawing or electron-donating substituents in the linkages of symmetric COFs can lead to efficient charge separation as well as appropriate HOCO and LUCO positions of the generated COFs for specific photocatalytic reactions.The proposed rule can be utilized to further boost the photocatalytic performance of many symmetric COFs.

Structures and reactivities of the CeO2/Pt(111)reverse catalyst:A DFT+U study

For heterogeneous catalysts,the build-up of interface contacts can influence markedly their activities.Being different from the conventional supported metal/oxide catalysts,the reverse type of oxide/metal structures,e.g.the ceria/Pt composite,have emerged as novel catalytic materials in many fields.However,it remains challenging to determine the optimal interface structure and/or the metal-oxide synergistic effect that can boost catalytic activities.In this work,we conducted density functional theory calculations with on-site Coulomb interaction correction to determine the optimal structures and investigate the physical as well as catalytic properties of various Ce O2/Pt(111)composites containing Ce O2(111)monolayer,bilayer,and trilayer at Pt(111).We found that the interaction strength between Ce O2(111)and Pt(111)substrate first reduces as the ceria slab grows from monolayer to bilayer,and then largely gets converged when the trilayer occurs.Such trend was well rationalized by analyzing the number and distances of O–Pt bonds at the interface.Calculated Bader charges uncovered the significant charge redistribution occurring around the interface,whereas the net electron transfer across the interface is non-significant and decreases as ceria thickness increases.Moreover,comparative calculations on oxygen vacancy formation energies clarified that oxygen removal can be promoted on the Ce O2/Pt(111)composites,especially at the interface.We finally employed CO oxidation as a model reaction to probe the surface reactivity,and determined an intrinsic activity order of monolayer Ce O2(111)>monolayer Ce O2(111)/Pt(111)>regular Ce O2(111).More importantly,we emphasized the significant role of the moderate ceria-Pt interaction at the interface that endows the Ce O2/Pt reverse catalyst both good thermostability and high catalytic activity.The monolayer Ce O2(111)/Pt(111)composite was theoretically predicted highly efficient for catalyzing CO oxidation.

A novel heterogeneous Co(Ⅱ)-Fenton-like catalyst for efficient photodegradation by visible light over extended pH

A novel Co^Ⅱ-Fenton-like heterogeneous catalyst,(H3O)2[Co^Ⅱ(phen)(H2O)2]2[Mo^Ⅵ5O15(PO4)2]·4H2O (phen=1,10-phenanthroline,C12N2H8)(1),is synthesized and utilized for photocatalytic degradation of organic dyes and antibiotic in a wide range of pH.The experimental results show that 1 acting as the Fenton-like catalyst with H2O2 exhibits remarkable activity at pH 3–9 under vis-light irradiation and is merited with excellent recyclability and reusability.A variety of analytical methods,including in-situ electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT) calculations,are applied to study the mechanism on generation of·OH and O2^·-radicals for photocatalytic degradation.It suggests that,unlike the classical Fenton process involving the redox transformation of the central cations,the generation of·OH and O2^·-radicals is associated with the substitution of the coordinating water molecules at Co(Ⅱ) by H2O2 and/or OOH^-,followed by the light-driven O–O bond cleavage and dissociation.The outcomes of this study are striking which overcome the obstacles in the classical Fe^Ⅱ-Fenton process,including the slow redox transformation between Fe(Ⅱ) and Fe(Ⅲ) and the production of massive iron precipitates especially at elevated pH.It opens up new avenues for the development of the high-performance Fenton(-like) catalysts for photocatalytic degradation over extended pH and provides new insight into the related process.

Theoretical insight into methanol steam reforming on indium oxide with different coordination environments

Indium oxide(In_2O_3) has demonstrated to be an effective non-noble metal catalyst for methanol steam reforming reaction(MSR).However, the reaction mechanism of MSR and crucial structure-activity relations determining the catalytic performance of In_2O_3 are still not fully understood yet. Using density functional theory(DFT) calculation, we systematically investigate the MSR process over a high-index In_2O_3(211) and a favoured catalytic cycle of MSR is determined. The results show that In_2O_3(211) possesses excellent dehydrogenation and oxidizing ability, on which CH_3 OH can readily adsorb on the In4 c site and be easily activated by the reactive lattice oxygens, resulting in a total oxidation into CO_2 rather than CO, while the H_2 formation through surface H–H coupling limits the overall MSR activity because of the strong H adsorption on the two-coordinated lattice O(O_(2c)). Our analyses show that the relatively inert three-coordinated lattice O(O_(3c)) could play an important catalytic role. To uncover the influence of the local coordination of surface In atoms and lattice O on the catalytic activity, we evaluate the activity trend of several types of In_2O_3 surfaces including(211),(111), and(100) by examining the rate-limiting, which reveals the following activity order:(211)>(111)>(100). These findings provide an in-depth understanding on the MSR reaction mechanism over In_2O_3 catalysts and some basic structure-activity relations at the atomic scale, could facilitate the rational design of In_2O_3-based catalysts for MSR by controlling the local coordination environment of surface active sites.

A DFT study of the CO adsorption and oxidation at ZnO surfaces and its implication for CO detection

Recently,ZnO-based gas sensors have been successfully fabricated and widely studied for their excellent sensitivity and selectivity,especially in CO detection.However,detailed explorations of their mechanisms are rather limited.Herein,aiming at clarifying the sensing mechanism,we carried out density functional theory(DFT)calculations to track down the CO adsorption and oxidation on the ZnO(1010)and(1120)surfaces.The calculated results show that the lattice O of ZnO(1010)is more reactive than that of ZnO(1120)for CO oxidation.From the calculated energetics and structures,the main reaction product on both surfaces can be determined to be CO2 rather than carbonate.Moreover,the surface conductivity changes during the adsorption and reaction processes of CO were also studied.For both ZnO(1010)and(1120),the conductivity would increase upon CO adsorption and decrease following CO oxidation,in consistence with the reported experimental results.This work can help understand the origins of ZnO-based sensors’performances and the development of novel gas sensors with higher sensitivity and selectivity.

Relationships between the activities and Ce^(3+)concentrations of CeO_(2)(111)for CO oxidation:A first-principle investigation

CO oxidation at ceria surfaces has been studied for decades,and many efforts have been devoted to understanding the effect of surface reduction on the catalytic activity.In this work,we theoretically studied the CO oxidation on the clean and reduced CeO_(2)(111)surfaces using different surface cells to dete rmine the relationships between the reduction degrees and calculated reaction energetics.It is found that the calculated barrier for the direct reaction between CO and surface lattice O drastically decreases with the increase of surface reduction degree.From electronic analysis,we found that the surface reduction can lead to the occurrence of localized electrons at the surface Ce,which affects the charge distribution at surface O.As the result,the surface O becomes more negatively charged and therefore more active in reacting with CO.This work then suggests that the localized 4 f electron reservoir of Ce can act as the"pseudo-anion"at reduced CeO_(2) surfaces to activate surface lattice O for catalytic oxidative reactions.

FeOOH photo-deposited perylene linear polymer with accelerated charge separation for photocatalytic overall water splitting

It is a challenge to develop single polymer-based photocatalyst for overall water splitting without adding sacrificial agents due to the insufficient driving force for charge separation and the lack of active sites of organic polymer.Metal oxyhyroxides are widely acted as co-catalyst for photoelectrocatalysis oxygen evolution reaction.Here,we firstly report the peryleno[1,12-bcd]thiophene sulfone-based linear co-polymer PS-5 for photocatalytic overall water splitting by photo-depositing simple and low-cost cocatalyst FeOOH under the visible-light illumination.The density functional theory(DFT)calculations and experimental results indicated clearly that the oxygen vacancies-richβ-FeOOH can effectively promote the separation of photo-generated excitons and provide active sites for photocatalytic oxygen evolution reaction.As a result,the average H_(2)and O_(2)production rates of optimized PS-5/β-FeOOH-0.2M reach at~170 and~76.6μmol h^(-1)g^(-1),respectively,with a stoichiometric ratio at about 2:1.This work provides a simple and low-cost method for the preparation of overall water splitting system based on polymer photocatalyst.

Screening performance of methane activation over atomically dispersed metal catalysts on defective boron nitride monolayers:A density functional theory study

Methane(CH_(4))controllable activation is the key process for CH_(4)upgrading,which is sensitive to the surface oxygen species.The high thermal conductivity and superb thermal stability of the hexagonal boron nitride(h-BN)sheet makes a single transition metal atom doped hexagonal boron nitride monolayer(TM-BN)possible to be a promising material for catalyzing methane partial oxidation.The performances of 24 TM-BNs for CH_(4)activation are systematically investigated during the CH_(4)oxidation by means of first-principles computation.The calculation results unravel the periodic va riation trends for the stability of TM-BN,the adsorption strength and the kind of O_(2)species,and the resulting CH_(4)activation performance on TM-BNs.The formed peroxide O_(2)^(2-)of which the O-O bond could be broken and O-anions are found to be reactive oxygen species for CH_(4)activation under the mild conditions.It is found that the redox potential of TM center,including its valence electron number,coordination environment,and the work function of TM-BN,is the underlying reason for the formation of different oxygen species and the resulting activity for CH_(4)oxidative dehydrogenation.

Pd single-atom monolithic catalyst: Functional 3D structure and unique chemical selectivity in hydrogenation reaction

Regulating the selectivity of catalysts in selective hydrogenation reactions at the atomic level is highly desirable but remains a grand challenge. Here we report a simple and practical strategy to synthesize a monolithic single-atom catalyst(SAC) with isolated Pd atoms supported on bulk nitrogen-doped carbon foams(Pd-SAs/CNF). Moreover, we demonstrate that the single-atom Pd sites with unique electronic structure endow Pd-SAs/CNF with an isolated site effect, leading to excellent activity and selectivity in 4-nitrophenylacetylene semi-hydrogenation reaction. In addition, benefiting from the great integrity and excellent mechanical strength, monolithic Pd-SAs/CNF catalyst is easy to separate from the reaction system for conducting the subsequent recycling. The cyclic test demonstrates the excellent reusability and stability of monolithic Pd-SAs/CNF catalyst.The discovery of isolated site effect provides a new approach to design highly selective catalysts. And the development of monolithic SACs provides new opportunities to advance the practical applications of single-atom catalysts.

Insight into room-temperature catalytic oxidation of NO by CrO_2(110):A DFT study

The NO oxidation processes on CrO_2(110) was investigated by virtue of DFT + U calculation together with microkinetic analysis, aiming to uncover the reaction mechanism and activity-limiting factors for CrO_2 catalyst. It was found that NO oxidation on CrO_2(110) has to be triggered with the lattice Obri involved(Mars-van Krevelen mechanism) rather than the Langmuir-Hinshelwood path occurring at the Cr_(5 c) sites alone. Specifically, the optimal reaction path was identified. Quantitatively, the microkinetic analysis showed that CrO_2(110) can exhibit a high turnover rate of 0.978 s^(-1) for NO oxidation at room temperature.Such an activity could originate from the bifunctional synergetic catalytic mechanism, in which the Cr_(5c)sites can exclusively adsorb NO and the Obri is very reactive and provides oxidative species. However, it is worth noting that, as the reactive Obri tightly binds NO_2, the nitrate species was found to be difficult removed and constituted the key poisoning species, eventually limiting the overall activity of CrO_2. This work demonstrated the considerable catalytic ability of CrO_2 for NO oxidation at room temperature, and the understanding may facilitate the further design of more active Cr-based catalyst.

First principles study of Fenton reaction catalyzed by FeOCl:reaction mechanism and location of active site

Fe-based solid catalysts in promoting Fenton reaction to generate ·OH radical has drawn much attention,and interestingly,FeOCl was reported to have superior activity compared with the traditional Fe2 O3 catalysts.However,the mechanism of Fenton reaction on FeOCl and the origin of high activity remain unclear.Herein,by virtue of DFT+ U calculations,the H2 O2 decomposition and conversion mechanism on FeOCl(100)surface were systematically investigated.It is found that on clean FeOCl(100)surface,the exposed[Fe^3+-Fe^3+]sites can hardly break O-O bond of H2 O2 into OH groups,but instead H2 O2 tends to dehydrogenate by the surface lattice O,resulting in a series of side reactions and final conversion into O2,while the left H atoms gradually saturate the surface lattice O and reduce Fe^3+ into Fe^2+.On fully H-covered FeOCl(100),H2O2 can efficiently dissociate at[Fe^2+-Fe^2+]sites into two OH,but OH binds with Fe^2+ so strongly that it cannot desorb as OH radical as easily as that on Fe^3+.Interestingly,FeOCl(100)tends to be partially protonated in the real acid solution,which,along with H2 O2 dehydrogenation,results in the formation of active unit [Fe^2+-Fe^3+].On[Fe^2+-Fe^3+]unit,H2 O2 can easily break its O-O bond and OH at Fe3+ can desorb as OH radical,while the other OH at Fe^2+ couples with the surface H into H2O and finish the catalytic cycle.By comparison,Fe2 O3(012)cannot provide enough [Fe^2+-Fe^3+] active units due to the relative difficulty in H2 O2 dehydrogenation,which accounts for its inferior catalytic efficiency for Fenton reaction.

Identifying the composition and atomic distribution of Pt-Au bimetallic nanoparticle with machine learning and genetic algorithm

Bimetallic nanoparticles(AmBn)usually exhibit rich catalytic chemistry and have drawn tremendous attention in heterogeneous catalysis.However,challenged by the huge configuration space,the understanding toward their composition and distribution of A/B element is known little at the atomic level,which hinders the rational synthesis.Herein,we develop an on-the-fly training strategy combing the machine learning model(SchNet)with the genetic algorithm(GA)search technique,which achieve the fast and accurate energy prediction of complex bimetallic clusters at the DFT level.Taking the 38-atom PtmAu38-mnanoparticle as example,the element distribution identification problem and the stability trend as a function of Pt/Au composition is quantitatively re solved.Specifically,results show that on the Pt-rich cluster Au atoms prefer to occupy the low-coordinated surface corner sites and form patch-like surface segregation patte rns,while for the Au-rich ones Pt atoms tend to site in the co re region and form the co re-shell(Pt@Au)configuration.The thermodynamically most stable PtmAu38-mcluster is Pt6 Au32,with all the core-region sites occupied by Pt,rationalized by the stronger Pt-Pt bond in comparison with Pt-Au and Au-Au bonds.This work exemplifies the potent application of rapid global sea rch enabled by machine learning in exploring the high-dimensional configuration space of bimetallic nanocatalysts.

The critical role of electrochemically activated adsorbates in neutral OER

Developing efficient electrocatalysts for the oxygen evolution reaction(OER)under neutral conditions is important for microbial electrolysis cells(MECs).However,the OER kinetics in neutral electrolytes at present are extremely sluggish,resulting in high overpotentials that greatly limit the energy conversion efficiencies of MECs.Previous studies failed to probe the adsorbates on surface metal sites of catalysts at the atomic scale and elucidate their influence on the catalytic activities,which has impeded the rational design of efficient neutral OER catalysts with optimal surface structures.Here,using in situ transmission electron microscopy(TEM),in situ X-ray photoelectron spectroscopy(XPS)and in situ low-energy ion scattering studies,we have identified,for the first time,that the electrochemically activated adsorbates on surface metal sites play a critical role in boosting the neutral OER activities of Ru-Ir binary oxide(RuxIryO2)catalysts.The adsorbate-activated RuxIryO2on a glassy carbon electrode achieved a low overpotential of 324 m V at10 m A cm-2in neutral electrolyte,with a 36-fold improvement in turnover frequency compared with that of Ir O2benchmark.Upon application in an MEC system,the resulting full cell showed a decreased voltage of 1.8 V,200 m V lower than the best value reported to date,facilitating efficient synthesis of poly(3-hydroxybutyrate)from bioelectrochemical CO2reduction.Density functional theory(DFT)studies revealed that the enhanced OER activity of RuxIryO2catalyst arose from local structural distortion of adjacent adsorbate-covered Ru octahedra at the catalyst surface and the consequently decreased adsorption energies of OER intermediates on Ir active center.

Genetic algorithm aided density functional theory simulations unravel the kinetic nature of Au(100) in catalytic CO oxidation

Heterogeneous catalysis is of tremendous importance to modern industries. Exposed atoms of heterogeneous catalysts are heavily involved in surface processes such as the adsorption, activation, diffusion and reaction of substrate molecules. Surfaces of metal or metal oxide based catalysts are usually taken as hard templates that only undergo limited relaxation during catalytic reactions, especially in theoretical simulations. In this work, by using genetic algorithm (GA) aided density functional theory (DFT) calculations, we studied the surface processes involved in CO oxidation on the Au(100) surface. The use of GA greatly improves the capacity of DFT calculations in locating the potential energy surface (PES) of the surface reactions, and surprisingly, it has been found that the Au(100) surface can undergo drastic reconstruction under the influence of O adsorption and the adapted partially oxidized Au surface exhibits unique activities for subsequent adsorptions and reactions. This work depicts the kinetic nature of the Au (100) surface in its catalyzed reactions and also significantly expands our understanding of how surface atoms act in heterogeneous catalysis.

Influence of Cl substitution on the electronic structure and catalytic activity of ceria

Cl-containing cerium dioxide(Ce O2) catalysts have been found to exhibit unique catalytic activities. In the present work, using density functional theory calculations with the inclusion of on-site Coulomb correction, we systematically studied the effect of Cl on the physicochemical properties of Ce O2 surfaces by substituting one subsurface O with Cl. The calculated results show that substituting an O atom with a Cl atom results in structural distortion and the reduction of one surface Ce4+ cation to Ce3+. The protruding Ce3+ cation greatly improves the adsorption energy of O2 to produce an active O2- species, and maintains the catalytic oxidation cycle of CO on Ce O2(110). These results may help us obtain a better understanding of Cl-ceria interacting systems and provide some guidance for the design of effective Ce O2-based catalysts.