Enhancing sintering resistance of atomically dispersed catalysts in reducing environments with organic monolayers

Atomically dispersed precious metal catalysts maximize atom efficiency and exhibit unique reactivity.However,they are susceptible to sintering.Catalytic reactions occurring in reducing environments tend to result in atomically dispersed metals sintering at lower temperatures than in oxidative or inert atmospheres due to the formation of mobile metal-H or metal-CO complexes.Here,we develop a new approach to mitigate sintering of oxide supported atomically dispersed metals in a reducing atmosphere using organophosphonate self-assembled monolayers(SAMs).We demonstrate this for the case of atomically dispersed Rh on Al_(2)O_(3) and TiO_(2) using a combination of CO probe molecule FTIR,temperature programmed desorption,and alkene hydrogenation rate measurements.Evidence suggests that SAM functionalization of the oxide provides physical diffusion barriers for the metal and weakens the interactions between the reducing gas and metal,thereby discouraging the adsorbate-promoted diffusion of metal atoms on oxide supports.Our results show that support functionalization by organic species can provide improved resistance to sintering of atomically dispersed metals with maintained catalytic reactivity.

Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Atomic Dispersed Hetero‑Pairs for Enhanced Electrocatalytic CO_(2)Reduction

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.

Atomically Dispersed Dual‑Metal Sites Showing Unique Reactivity and Dynamism for Electrocatalysis

The real structure and in situ evolution of catalysts under working conditions are of paramount importance,especially for bifunctional electrocatalysis.Here,we report asymmetric structural evolution and dynamic hydrogen-bonding promotion mechanism of an atomically dispersed electrocatalyst.Pyrolysis of Co/Ni-doped MAF-4/ZIF-8 yielded nitrogen-doped porous carbons functionalized by atomically dispersed Co–Ni dual-metal sites with an unprecedented N8V4 structure,which can serve as an efficient bifunctional electrocatalyst for overall water splitting.More importantly,the electrocatalyst showed remarkable activation behavior due to the in situ oxidation of the carbon substrate to form C–OH groups.Density functional theory calculations suggested that the flexible C–OH groups can form reversible hydrogen bonds with the oxygen evolution reaction intermediates,giving a bridge between elementary reactions to break the conventional scaling relationship.

Effects of Dispersed Mo-Fe Catalysts on Catalytic Hydrothermal Conversion of Residue

Replacement of precious single metal catalysts with cost-effective,highly-dispersed composite catalysts for catalytic hydrothermal conversion of residue holds tremendous promise for the residue upgrading technologies.Organic metals were added to the feed as the oil-soluble precursors,and were transformed into the catalytic active phases in this work.Physical properties and structures of the composite catalysts had been investigated by X-ray fluorescence spectroscopy,X-ray photoelectron spectroscopy,X-ray diffraction,scanning electron microscopy and transmission electron microscopy.The composite catalysts were found to be highly efficient in the catalytic hydrothermal conversion of both the model compound and the residue.Increased metal dispersion and synergistic effects of two metals played indispensable roles in such catalytic system.Results showed that under the test conditions specified in the article,the catalyst had the best catalytic performance when the mass ratio of molybdenum to iron was 1.5.

The reformation of catalyst:From a trial-and-error synthesis to rational design

The appropriate catalysts can accelerate the reaction rate and effectively boost the efficient conversion of various molecules,which is of great importance in the study of chemistry,chemical industry,energy,materials and environmental science.Therefore,efficient,environmentally friendly,and easy to operate synthesis methods have been used to prepare various types of catalysts.Although previous studies have reported the synthesis and characterization of the aforementioned catalysts,more still remain in trial and error methods,without in-depth consideration and improvement of traditional synthesis methods.Here,we comprehensively summarize and compare the preparation methods of the trial-and-error synthesis strategy,structure–activity relationships and density functional theory(DFT)guided catalysts rational design for nanomaterials and atomically dispersed catalysts.We also discuss in detail the utilization of the nanomaterials and single atom catalysts for converting small molecules(H_(2)O,O_(2),CO_(2),N_(2),etc.)into value-added products driven by electrocatalysis,photocatalysis,and thermocatalysis.Finally,the challenges and outlooks of mass preparation and production of efficient and green catalysts through conventional trial and error synthesis and DFT theory are featured in accordance with its current development.

Supported Atomically Dispersed Pd Catalyzed Direct Alkoxylation and Allylic Alkylation

A new approach to allylic alkylation is realized using an atomically dispersed palladium catalyst(Pd1/TiO2-EG).Unlike conventional methods that require derivation of substrates and utilization of additives,this method allows for direct allylic alkylation from allylic alcohols,producing H2O as the sole by-product.The catalyst's high efficiency is attributed to the local hydrogen bonding at the or-ganic-inorganic interface(Pd-EG interface),facilitating hydroxyl group activation forη3π-allyl complex formation.The system demonstrates successful direct C—O and C—C coupling reactions with high selectivity,requiring no additives.This study highlights the potential of supported atomically dispersed catalysts for greener and more efficient catalysis,meanwhile,offers unique insights into the distinct behavior of atomically dispersed catalysts in comparison to homogeneous or nanoparticle-based catalysts.

Synthesis of atomically dispersed cationic nickel-confined mesoporous ZSM-48(ANMZ-48)directed by metal complexes in amphiphilic molecules

The synthesis of mesoporous zeolite-anchored atomically dispersed metal catalysts(ADCs)is a considerable challenge in chemistry and materials science.Here we report the synthesis of atomically dispersed cationic nickel-confined mesoporous ZSM-48(ANMZ-48)by in situ hydrothermal reaction employing a designed tri-functional metal complex template,by which the triquaternary ammonium groups in the hydrophilic region direct the formation of ZSM-48 zeolite;the aromatic groups in the hydrophobic tail generate the mesopores through π-π stacking;and the complexes formed by nickel ions coordinated with terpyridyl groups generate atomically dispersed Ni2+confined in zeolite frameworks due to the strong sintering resistance generated by the strong coordination interaction.The ANMZ-48 is consisting of stacking of sheet-like ZSM-48 domains connected by multiply crystal twinning sharing the common(011)plane,generating abundant of imbedded mesopores with the uniform thickness of~2.4 nm and with the width of 10-50 nm.The excellent catalytic activity and stability of ANMZ-48 were also reflected in the dry reforming of methane(DRM)reaction.

Cu_(2)O-SupportedAtomicallyDispersed Pd Catalysts for Semihydrogenation of Terminal Alkynes: Critical Role of Oxide Supports

Atomically dispersed catalysts have demonstrated superior catalytic performance in many chemical transformations.However,limited success has been achieved in applying oxide-supported atomically dis-persed catalysts to semihydrogenation of alkynes under mild conditions.

Stabilizing highly active atomically dispersed NiN_(4)Cl sites by Cl-doping for CO_(2)electroreduction

Nickel-nitrogen-carbon single-atom catalysts have attracted widespread interest for CO_(2)electroreduction but they suffer from poor stability.Herein,we report on the preparation of Cl-and N-doped porous carbon nanosheets with atomically dispersed NiN_(4)Cl active sites(NiN_(4)Cl-ClNC)through a molten-salt-assisted pyrolysis strategy.The optimized NiN_(4)Cl-ClNC catalyst delivers exceptional CO_(2)conversion activity with outstanding stability for over 220 h at−0.7 V versus RHE and a high CO Faradaic efficiency of 98.7%at a CO partial current density of 12.4 mA cm^(−2).Moreover,NiN_(4)Cl-ClNC displays a remarkable CO partial current density of approximately 349.4 mA cm^(−2)in flow-cell,meeting the requirements of industrial applications.Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy and density functional theory calculations are used to understand the outstanding activity and stability.Results reveal that the introduced axial Ni-Cl bond on the Ni center and Cl─C bond on the carbon support synergetically induce electronic delocalization,which not only stabilizes Ni against leaching but also facilitates the formation of the COOH*intermediate that is found to be the rate-determining step.

High-temperature treatment to engineer the single-atom Pt coordination environment towards highly efficient hydrogen evolution

Development of high-performance and cost-effective catalysts for electrocatalytic hydrogen evolution reaction(HER)play crucial role in the growing hydrogen economy.Recently,the atomically dispersed metal catalysts have attracted increasing attention due to their ultimate atom utilization and great potential for highly cost-effective and high-efficiency HER electrocatalyst.Herein,we propose a hightemperature treatment strategy to furtherly improve the HER performance of atomically dispersed Ptbased catalyst.Interestingly,after appropriate high-temperature treatment on the atomically dispersed Pt0.8@CN,the Pt species on the designed N-doped porous carbon substrate with rich defect sites can be re-dispersed to single atom state with new coordination environment.The obtained Pt0.8@CN-1000 shows superior HER performance with overpotential of 13 m V at 10 m A cm^(-2)and mass activity of 11,284 m A/mgPtat-0.1 V,much higher than that of the pristine Pt0.8@CN and commercial Pt/C catalyst.The experimental and theoretical investigations indicate that the high-temperature treatment induces the restructuring of coordination environment and then the optimized Pt electronic state leads to the enhanced HER performances.This work affords new strategy and insights to develop the atomically dispersed high-efficiency catalysts.

Nested Metal Catalysts:Metal Atoms and Clusters Stabilized by Confinement with Accessibility on Supports

Supported catalysts that are important in technology prominently include atomically dispersed metals and metal clusters.When the metals are noble,they are typically unstablesusceptible to sinteringespecially under reducing conditions.Embedding the metals in supports such as organic polymers,metal oxides,and zeolites confers stability on the metals but at the cost of catalytic activity associated with the lack of accessibility of metal bonding sites to reactants.An approach to stabilizing noble metal catalysts while maintaining their accessibility involves anchoring them in molecular-scale nests that are in or on supports.The nests include zeolite pore mouths,zeolite surface cups(half-cages),raft-like islands of oxophilic metals bonded to metal oxide supports,clusters of non-noble metals(e.g.,hosting noble metals as single-atom alloys),and nanoscale metal oxide islands that selectively bond to the catalytic metals,isolating them from the support.These examples illustrate a trend toward precision in the synthesis of solid catalysts,and the latter two classes of nested catalysts offer realistic prospects for economical large-scale application.

Hierarchical peony-like FeCo-NC with conductive network and highly active sites as efficient electrocatalyst for rechargeable Zn-air battery

Carbon materials featuring hierarchical pores and atomically dispersed metal sites are promising catalysts for energy storage and conversion applications.Herein,we developed a facile strategy to construct functional carbon materials with a fluffy peony-like structure and dense binary FeCo-Nx active sites(termed as f-FeCo-CNT).By regulating the metal content in precursors,a three-dimensional(3D)interconnected conductive carbon nanotubes network was in-situ formed throughout the atomically dispersed FeCo-NC matrix during pyrolysis.Taking advantage of rich pore hierarchy and co-existence of highly active FeCo-Nx sites and beneficial FeCo alloy nanoparticles,the f-FeCo-CNT material exhibited excellent bifunctional performance towards oxygen reduction reaction/oxygen evolution reactions(ORR/OER)with respect to the atomically dispersed FeCo-NC(SA-f-FeCo-NC)and commercial Pt/C+Ru02 mixture,surpassing the SA-f-FeCo-NC with a 20 mV higher ORR half-wave potential and a 100 mV lower OER overpotential(at 10.0 mA/cm^2).Remarkably,the f-FeCo-CNT-assembled Zn-air battery(ZAB)possessed a maximum specific power of 195.8 mW/cm^2,excellent rate capability,and very good cycling stability at large current density of 20.0 mA/cm^2.This work provides a facile and feasible synthetic strategy of constructing low-cost cathode materials with excellent comprehensive ZAB performance.

Effect of active oxygen on the performance of Pt/CeO2 catalysts for CO oxidation

This study was focused on the influence of active oxygen on the performance of Pt/CeO2 catalysts for CO oxidation. A series of CeO2 supports with different contents of active oxygen were obtained by adding surfactant at different synthesis steps. 0.25 wt% Pt was loaded on these CeO2 supports by incipientwetness impregnation methods. The catalysts were characterized by N2 adsorption, X-ray diffraction（XRD）, high-resolution transmission electron microscopy（HRTEM）, H2 temperature-programmed reduction（H2-TPR）, dynamic oxygen storage capacity（DOSC） and in-situ DRIFTS technologies. For S-f supports, the surfactant was added into the solution before spray-drying in the synthesis process, which facilitates more active oxygen formation on the surface of CeO2. After loading Pt, the more active oxygen on CeO2 contributes to dispersing Pt species and enhancing the CO oxidation activity. As for the aged samples,Pt-R-h shows the highest activity above 190 ℃ because of the presence of more partly oxidized Pt^（δ＋） species. Thus the activity is also influenced by the states of Pt and the Pt^（δ＋） species may contribute to the high activity at elevated temperature.

Effects of Ce on catalytic combustion of methane over Pd-Pt/Al_2O_3 catalyst

Activity and stability of 1%Pd-0.2%Pt/Al2O3 and 1%Pd-0.2%Pt/0.6%Ce/Al2O3 catalysts prepared by impregnation method for catalytic combustion of methane in air were investigated. The catalysts before and after reaction were characterized by BET, CO chemisorption, XRD and XPS techniques. Results showed that the presence of Ce significantly increased the activity and thermal stability of the Pd-Pt/Al2O3 catalyst towards methane combustion, which could be attributed to more highly-dispersed active PdO particles over the Pd-Pt/Ce/Al2O3 catalyst surface as well as the retarded sintering of PdO and the maintained oxidized state of surface Pd during the combustion process in the presence of Ce.

Synergy of Fe-N4 and non-coordinated boron atoms for highly selective oxidation of amine into nitrile

The rational design of highly active and stable atomically dispersed M-X4(M=Fe,Co,Ni,etc.,X=C,N)-based catalysts holds promises for wide application in almost all realms of catalysis.Despite great effort in the construction of specific M-X4 centers,the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored.Herein,we develop a new type of M-X4 catalyst composed of Fe-N4 centers and non-coordinated B heteroatoms(FeNC+B)and find the key role of non-coordinated B adjacent to Fe-N4 centers in tailoring their electron density and final catalytic selectivity.The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N4 centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines.As a reusable heterocatalyst,the state-of-the-art FeNC+B catalyst provides a turn-over frequency(TOF)value of 21.6 molbenzonitrile·molFe^−1·h^−1(100℃),outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.

Surface Organometallic Chemistry for Single-site Catalysis and Single-atom Catalysis

Although driven by different research interests,single-site catalysts and single-atom catalysts are both believed to be model systems bridging homogeneous and heterogeneous catalysis.The two concepts are similar but different.In this review,we will first explain the difference between single-atom catalysis and single-site catalysis,in terms of their goals,synthetic methods and coordination structures of corresponding catalysts.Then,we will introduce the surface organometallic chemistry method,a method traditionally used for synthesizing single-site catalyst.We will explain why it might benefit the single-atom catalysis community.At last,the choice of support to accommodate the method for synthesizing single-atom catalysts will be discussed.

Kinetically rate-determining step modulation by metal-support interactions for CO oxidation on Pt/CeO_(2)

Rational design and performance promotion are eternal topics and ultimate goals in catalyst preparation.In contrast,trial–and–error is still the common method people take.Therefore,it is important to develop methods to intrinsically enhance the performance of catalysts.The most effective solutions are the one from a kinetic perspective based on clear knowledge of the reaction mechanism.This paper describes rate-determining step cognition and modulation to promote CO oxidation on highly dispersed Pt on CeO_(2).The different degrees of metal–support interactions due to variation of hydroxyl density of support could alter the structure of active species and the ability of oxygen activation apparently,further shift the rate-determining step from oxygen activation to oxygen reverse spillover kinetically.The transformation of rate-determining step could enhance the intrinsic activity significantly,and decrease the T_(50) approximately 140℃.The findings of this research exemplify the universal and effective method of performance elevation by rate-determining step modulation,which is promising for application in different systems.