Tandem catalysis for enhanced CO oxidation over the Bi-Au-SiO_(2)interface

Bimetallic catalysts typically exploit unique synergetic effects between two metal species to achieve their catalytic effect.Understanding the mechanism of CO oxidation using hybrid heterogeneous catalysts is important for effective catalyst design and environmental protection.Herein,we report a Bi-Au/SiO_(2)tandem bimetallic catalyst for the oxidation of CO over the Au/SiO_(2)surface,which was monitored using near-ambient-pressure X-ray photoelectron spectroscopy.The Au-decorated SiO_(2)catalyst exhibited scarce activity in the CO oxidation reaction;however,the introduction of Bi to the Au/SiO_(2)system promoted the catalytic activity.The mechanism is thought to involve the dissociation O_(2)molecules in the presence of Bi,which results in spillover of the O species to adjacent Au atoms,thereby forming Au^(δ+).Further CO adsorption,followed by thermal treatment,facilitated the oxidation of CO at the Au-Bi interface,resulting in a reversible reversion to the neutral Au valence state.Our work provides insight into the mechanism of CO oxidation on tandem surfaces and will facilitate the rational design of other Au-based catalysts.

Tandem Lewis acid catalysis for the conversion of alkenes to 1,2‐diols in the confined space of bifunctional TiSn‐Beta zeolite

The generation of multifunctional isolated active sites in zeolite supports is an attractive method for integrating multistep sequential reactions into a single‐pass tandem catalytic reaction.In this study,bifunctional TiSn‐Beta zeolite was prepared by a simple and scalable post‐synthesis approach,and it was utilized as an efficient heterogeneous catalyst for the tandem conversion of alkenes to 1,2‐diols.The isolated Ti and Sn Lewis acid sites within the TiSn‐Beta zeolite can efficiently integrate alkene epoxidation and epoxide hydration in tandem in a zeolite microreactor to achieve one‐step conversion of alkenes to 1,2‐diols with a high selectivity of>90%.Zeolite confinement effects result in high tandem rates of alkene epoxidation and epoxide hydration as well as high selectivity toward the desired product.Further,the novel method demonstrated herein can be employed to other tandem catalytic reactions for sustainable chemical production.

Tandem catalysis on adjacent active motifs of copper grain boundary for efficient CO_(2) electroreduction toward C2 products

Copper (Cu) is a special electrocatalyst for CO_(2) reduction reaction (CO_(2)RR) to multi-carbon products.Experimentally introducing grain boundaries (GBs) into Cu-based catalysts is an efficient strategy to improve the selectivity of C^(2+) products.However,it is still elusive for the C^(2+) product generation on Cu GBs due to the complex active sites.In this work,we found that the tandem catalysis pathway on adjacent active motifs of Cu GB is responsible for the enhanced activity for C^(2+)production by first principles calculations.By electronic structure analysis shows,the d-band center of GB site is close to the Fermi level than Cu(100) facet,the Cu atomic sites at grain boundary have shorter bond length and stronger bonding with*CO,which can enhance the adsorption of*CO at GB sites.Moreover,CO_(2)protonation is more favorable on the region Ⅲ motif (0.84 e V) than at Cu(100) site (1.35 e V).Meanwhile,the region Ⅱ motif also facilitate the C–C coupling (0.72 e V) compared to the Cu(100) motif (1.09 e V).Therefore,the region Ⅲ and Ⅱ motifs form a tandem catalysis pathway,which promotes the C^(2+)selectivity on Cu GBs.This work provides new insights into CO_(2)RR process.

Differentially-grown cobalt regulators cooperatively involved in the tandem catalysis for high-yield production of second amines

One-pot tandem catalysis has been regarded as one of the most atomic economic ways to produce secondary amines,the important platform molecules for chemical synthesis and pharmaceutical manufacture,but it is facing serious issues in overall efficiency.New promotional effects are highly desired for boosting the activity and regulating the selectivity of conventional tandem catalysts.In this work,we report a high-performance tandem catalyst with maximized synergistic effect among each counterpart by preciously manipulating the spatial structure,which involves the active CeO_(2)/Pt component as kernel,the densely-coated N-doped C(NC)layer as selectivity controller,and the differentially-grown Co species as catalytic performance regulators.Through comprehensive investigations,the unique growth mechanism and the promotion effect of Co regulators are clarified.Specifically,the surface-landed Co clusters(Cocs)are crucial to selectivity by altering the adsorption configuration of benzylideneaniline intermediates.Meanwhile,the inner Co particles(Cops)are essential for activity by denoting their electrons to neighboring Ptps.Benefiting from the unique promotion effect,a remarkably-improved catalytic efficiency(100%nitrobenzene conversion with 94%N-benzylaniline selectivity)is achieved at a relatively low temperature of 80℃,which is much better than that of CeO_(2)/Pt(100%nitrobenzene conversion with 12%N-benzylaniline selectivity)and CeO_(2)/Pt/NC(35%nitrobenzene conversion with 94%benzylideneaniline selectivity).

Tandem catalysis of Cu/Ni multi-sites promotes oxygen reduction reaction

The special electronic characteristics and high atom usage efficiency of metal-nitrogen-carbon(M-N-C)materials have made them extremely attractive for oxygen reduction reactions(ORRs).However,it is inevitable that hydrogen peroxide(H_(2)O_(2))will be formed via the two-electron pathway in ORRs.Herein,the Cu nanoparticles(NPs)have been encapsulated into Ni doped hollow mesoporous carbon spheres(Ni-HMCS)to reduce the generation of H_(2)O_(2)in ORR.Electrochemical tests confirm that the introduction of Cu NPs improves the ORR performance greatly.The obtained Cu/Ni-HMCS exhibits a half-wave potential of 0.82 V vs.reversible hydrogen electrode and a limited current density of 5.5 mA cm^(-2),which is comparable with the commercial Pt/C.Moreover,Cu/Ni-HMCS has been used in Zn-air battery,demonstrating a high power density of 161 mW cm^(-2)and a long-term recharge capability(50 h at 5 mA cm^(-2)).The theoretical calculation proposes a tandem catalysis pathway for Cu/Ni multi-sites catalysis,that is,H_(2)O_(2)released from the Ni-N_(4)and Cu-N_(4)sites migrates to the Cu(111)face,on which the captive H_(2)O_(2)is further reduced to H_(2)O.This work demonstrates an interesting tandem catalytic pathway of dual-metal multi-sites for ORR,which provides an insight into the development of effective fuel cell electrocatalysts.

One-Pot Upgrading Polyethylene and CO_(2)to Aromatics via Tandem Catalysis

Polyolefins have the largest share in plastic waste,so it is vital to transform these end-of-life wastes into highly valued products.We present here a new catalytic method to produce aromatics using PE as a carbon source.Our results indicate that polyethylene(PE)and CO_(2)can be converted into aromatics and CO simultaneously,achieving a high transformation rate and a 64.0%selectivity toward aromatics below 400℃ by Cu-Fe_(3)O_(4)and Zn/ZSM-5 tandem catalysis.Notably,the established theoretical limit of 50%selectivity toward aromatics in PE aromatization is surpassed.This is attributed to the coexistence of reverse water-gas shift,which converts another feed,CO_(2),with hydrogen to produce valuable CO,confirmed by^(13)C isotope studies.It consumes excessive hydrogen generated during PE aromatization to produce CO and mitigates the production of light alkanes from hydrogen transfer reactions,thereby augmenting the formation of aromatic compounds.Our research offers a new approach to valorizing two prevalent waste carbon sources:waste plastic and CO_(2),which is useful for designing a new strategy for upcycling waste carbon resources.

Selective tandem hydrogenation and rearrangement of furfural to cyclopentanone over CuNi bimetallic catalyst in water

Tandem catalysis for the hydrogenation rearrangement of furfural(FA)provides an attractive solution for manufacturing cyclopentanone(CPO)from renewable biomass resources.The Cu-Ni/Al-MCM-41 catalyst was synthesized and afforded excellent catalytic performance with 99.0%conversion and 97.7%selectivity to CPO in a near-neutral solution under 2.0 MPa H2 at 160℃ for 5 h,much higher than those on other molecular sieve supports including MCM-41,SBA-15,HY,and ZSM-5.A small amount of Al highly dispersed in MCM-41 plays an anchoring role and ensures the formation of highly dispersed CuNi bimetallic nanoparticles(NPs).The remarkably improved catalytic performance may be attributed to the bimetallic synergistic and charge transfer effects.In addition,the initial FA concentration and the aqueous system pH required precise control to minimize polymerization and achieve high selectivity of CPO.Fourier transform infrared spectroscopy and mass spectra results indicated that polymerization was sensitive to pH values.Under acidic conditions,FA and intermediate furfuryl alcohol polymerize,while the intermediate 4-hydroxy-2-cyclopentenone mainly polymerizes under alkaline conditions,blocking the cascade of multiple reactions.Therefore,near-neutral conditions are most suitable for minimizing the impact of polymerization.This study provides a useful solution for the current universal problems of polymerization side reactions and low carbon balance for biomass conversion.

In situ reconstruction induced oxygen-deficient multiphase Cu based species hybridized with Ni single atoms as tandem platform for CO_(2) electroreduction

Tandem catalysis,capable of decoupling individual steps,provides a feasible way to build a high-efficiency CO_(2) electro-conversion system for multicarbons(C_(2+)).The construction of electrocatalytic materials is one of focusing issues.Herein,we fabricated a single atom involved multivalent oxide-derived Cu composite material and found it inclined to reconstruct into oxygen-deficient multiphase Cu based species hybridized with monatomic Ni on N doped C matrix.In this prototype,rapid CO generation and C-C coupling are successively achieved on NiN4 sites and surface amorphized Cu species with defects,resembling a micro-production line.In this way,the in situ formed tandem catalyst exhibited a high Faradaic efficiency(FE)of~78%for C_(2+)products along with satisfactory durability over 50 h.Particularly,the reconstruction-induced amorphous layer with abundant asymmetric sites should be favorable to improve the ethanol selectivity(FE:63%),which is about 10 times higher than that of the non-tandem Cu-based contrast material.This work offers a new approach for manipulating tandem catalyst systems towards enhancing C_(2+)products.

Tuning strategies and structure effects of electrocatalysts for carbon dioxide reduction reaction

Carbon dioxide emissions have increased due to the consumption of fossil fuels,making the neutralization and utilization of CO_(2) a pressing issue.As a clean and efficient energy conversion process,electrocatalytic reduction can reduce carbon dioxide into a series of alcohols and acidic organic molecules,which can effectively realize the utilization and transformation of carbon dioxide.This review focuses on the tuning strategies and structure effects of catalysts for the electrocatalytic CO_(2) reduction reaction(CO_(2)RR).The tuning strategies for the active sites of catalysts have been reviewed from intrinsic and external perspectives.The structure effects for the CO_(2)RR catalysts have also been discussed,such as tandem catalysis,synergistic effects and confinement catalysis.We expect that this review about tuning strategies and structure effects can provide guidance for designing highly efficient CO_(2)RR electrocatalysts.

Microfluidic assembly of WO_(3)/MoS_(2)Z-scheme heterojunction as tandem photocatalyst for nitrobenzene hydrogenation

Heterojunction-based photocatalyst plays an important role in the various heterogeneous catalyses.Z-scheme photocatalytic systems with two semiconductor materials are suitable for harvesting solar energy,while the advanced nanostructuring tools for the fabrication of Z-scheme heterojunction are limited.Here,WO_(3)/MoS_(2)(W/M_(0.2))heterojunction composites were constructed in a microfluidic system with enhanced assembly efficiency,and the photocatalytic performance has been investigated using X-ray photoelectron spectroscopy(XPS),MottSchottky(M-S)analysis and gas chromatograph-mass spectrometer(GC-MS).In addition,in the reduction of nitrobenzene,the photogenerated hole(h^(+))oxidation of formic acid(HCOOH)provides the hydrogen source and the deposited Pd nanoparticles are enriched with photogenerated electrons for improving the transfer hydrogenation efficiency.The microfluidic-prepared tandem photocatalyst gives a meaningful guidance for the design and synthesis of heterojunction catalysts,which is promising for energy maximizing control systems.

Tandem Catalysis of One Metallocene Catalyst Combined with Two Different Cocatalysts for Preparing Branched Polyethylene

Tandem catalytic systems, consisting of ethylene bis（indenyl） zirconium dichloride with two different cocatalysts, alkylaluminum（diethylaluminium chloride or trialkylaluminum） and methylaluminoxane, were employed in preparing branched polyethylene from ethylene as sole monomer. The catalytic system rac-Et（Ind）2Zr Cl2/Al Et2Cl/MAO exhibited high incorporation（29.0/1000C）. The oligomerization and copolymerization reaction conditions in the tandem catalytic system, as well as the different cocatalysts, have effects on the catalytic activity and the properties of the obtained polymer, such as melting temperature, crystallinity, molecular weight and molecular weight distribution. Moreover, the oligomerization reaction condition is the main factor in altering the properties and structures of polyethylene.

Bismuth clusters pinned on TiO_(2) porous nanowires boosting charge transfer for CO_(2) photoreduction to CH_(4)

Artificial photosynthesis in carbon dioxide(CO_(2))conversion into value-added chemicals attracts considerable attention but suffers from the low activity induced by sluggish separation of photogenerated carriers and the kinetic bottleneck-induced unsatisfied selectivity.Herein,we prepare a new-style Bi/TiO_(2) catalyst formed by pinning bismuth clusters on TiO_(2) nanowires through being confined by pores,which exhibits high activity and selectivity towards photocatalytic production of CH_(4) from CO_(2).Boosted charge transfer from TiO_(2) through Bi to the reactants is revealed via in situ X-ray photon spectroscopy and time-resolved photoluminescence(PL).Further,in situ Fourier transform infrared results confirm that Bi/TiO_(2) not only overcomes the multi-electron kinetics challenge of CO_(2) to CH_(4) via boosting charge transfer,but also facilitates proton production and transfer as well as the intermediates*CHO and*CH_(3)O generation,ultimately achieving the tandem catalysis towards methanation.Theoretical calculation also underlies that the more favorable reaction step from*CO to*CHO on Bi/TiO_(2) results in CH_(4) production with higher selectivity.Our work brings new insights into rational design of photocatalysts with high performance and the formation mechanism of CO_(2) to CH_(4) for solar energy storage in future.

Selectivity regulation of CO_(2)electroreduction on asymmetric AuAgCu tandem heterostructures

Rational design and synthesis of multimetallic nanostructures(NSs)are fundamentally important for electrochemical CO_(2)reduction reaction(CO_(2)RR).Herein,a multi-step seed-mediated growth method is applied to synthesize asymmetric AuAgCu heterostructures using Au nanobipyramids as nucleation seeds,in which their composition and structures are well controlled.We find that the selectivity of C_(2)products for CO_(2)RR could be effectively regulated by tandem catalysis and electronic effect over trimetallic AuAgCu heterostructures.Particularly,the Faraday efficiency toward ethanol could reach up to 37.5%at a potential of−0.8 V versus reversible hydrogen electrode over asymmetric Au1Ag1Cu5 heterostructures with segregated domains of three constituent metals.This work provides an efficient strategy for the synthesis of multicomponent architectures to boost their promising application in CO_(2)RR.

C1 Chemistry:The Stories of Research and Applications from Toyama

This review provides a comprehensive overview of the distinguished academic career and scientific accomplishments of Prof.Noritatsu Tsubaki at the University of Toyama.For over 35 years,he has dedicated himself to the research field of one-carbon(C1)chemistry,including catalytic conversion of C1 molecules to valuable chemicals and superclean fuels,innovative catalyst and reactor development,and the design of new catalytic reactions and processes.Organized chronologically,this review highlights Prof.Tsubaki’s academic contributions from 1990,when he studied and worked at The University of Tokyo,to his current role as a full professor at the University of Toyama.The academic section of this review is divided into three main parts,focusing on Prof.Tsubaki’s pioneering work in C1 chemistry.We believe that this review will serve as a highly valuable reference for colleagues in the fields of C1 chemistry and catalysis,and inspire the development of more original and groundbreaking research.

Atomically Precise Metal Nanoclusters as Single Electron Transferers for Hydroborylation

The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.

Upgrading ethylene via renewable energy-driven electrocatalysis

Ethylene oxide(EO)and ethylene glycol(EG)are two important commodity chemicals and are industrially produced from petroleum-derived ethylene via thermocatalytic processes.The overoxidation of ethylene and the implementation of high temperature and pressure lead to substantial CO_(2)emission.Renewable energy-driven electrocatalysis provides a low-carbon route for upgrading ethylene under mild conditions,especially when it couples with ethylene electrosynthesis from CO_(2).In this minireview,we summarize recent achievements in the selective electrocatalytic oxidation of ethylene to EO and EG.Three main reaction routes including direct electrocatalytic oxidation with water,indirect electrocatalytic oxidation with halide mediators,and tandem electrocatalytic and thermocatalytic oxidation with hydrogen peroxide intermediate,are discussed.Some representative catalyst systems and reactor designs are exemplified.We discuss the existing scientific and technical challenges of electrocatalytic ethylene upgrading in terms of reaction rate,selectivity,and long-term stability,and propose future research directions and opportunities for pushing the process towards practical application.

Recent progress in advanced core-shell metal-based catalysts for electrochemical carbon dioxide reduction

Electrochemical carbon dioxide reduction(CO_(2)RR)plays an important role in solving the problem of high concentration of CO_(2)in the atmosphere and realizing carbon cycle.Core-shell structure has many unique features including tandem catalysis,lattice strain effect,defect engineering,which exhibit great potential in electrocatalysis.In this review,we focus on the advanced core-shell metal-based catalysts(CMCs)for electrochemical CO_(2)RR.The recent progress of CMCs in electrocatalytic CO_(2)RR is described as the follow-ing aspects:(1)The mechanism of electrochemical CO_(2)RR and evaluation parameters of electrocatalyst performance,(2)preparation methods of core-shell metal catalysts and core-shell structural advantages and(3)advanced CMCs towards electrochemical CO_(2)RR.Finally,we make a brief conclusion and propose the opportunities and challenges in the field of electrochemical CO_(2)RR.