A review on electrocatalytic CO_(2) conversion via C-C and C-N coupling

Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.

Metal-organic-framework-derived copper-based catalyst for multicomponent C-S coupling reaction

Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.

Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions

To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.

d-d Orbital coupling induced by crystal-phase engineering assists acetonitrile electroreduction to ethylamine

The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.

Coupling Au with BO_(x) matrix induced by Closo-boron cluster for electrochemical synthesis of ammonia

Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.

Synthesis of N-Heterocyclic Carbine Silver(Ⅰ)and Palladium(Ⅱ)Complexes with Acylated Piperazine Linker and Catalytic Activity in Three Types of C-C Coupling Reactions

Main observation and conclusion Two bis-imidazolium salts LH_(2)·Cl_(2) and LH_(2)·(PF_(6))_(2) with acylated piperazine linker and two N-heterocyclic carbene(NHC)silver(Ⅰ)and palladium(Ⅱ)complexes[L_(2)Ag_(2)](PF_(6))_(2)(1)and[L_(2)Pd_(2)Cl_(4)](2)were prepared.The crystal structures of LH_(2)·Cl_(2) and 1 were confirmed by X-ray analysis.In 1,one 26-membered macrometallocycle was generated through two silver(Ⅰ)ions and two bidentate ligands L.The catalytic activity of 2 was investigated in Sonogashira,Heck-Mizoroki and Suzuki-Miyaura reactions.The results displayed that these C-C coupling reactions can be smoothly carried out under the catalysis of 2.

Recent advances in paired electrolysis coupling CO_(2) reduction with alternative oxidation reactions

Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the input energy is"wasted"at the anode due to the high overpotential requirement and the recovery of low-value oxygen.To make efficient use of the electricity during electrolysis,coupling CO_(2)RR with anodic alternatives that have low energy demands and/or profitable returns with high-value products is then promising.Herein,we review the latest advances in paired systems for simultaneous CO_(2) reduction and anode valorization.We start with the cases integrating CO_(2)RR with concurrent alternative oxidation,such as inorganic oxidation using chloride,sulfide,ammonia and urea,and organic oxidation using alcohols,aldehydes and primary amines.The paired systems that couple CO_(2)RR with on-site oxidative upgrading of CO_(2)-reduced chemicals are also introduced.The coupling mechanism,electrochemical performance and economic viability of these co-electrolysis systems are discussed.Thereby,we then point out the mismatch issues between the cathodic and anodic reactions regrading catalyst ability,electrolyte solution and reactant supply that will challenge the applications of these paired electrolysis systems.Opportunities to address these issues are further proposed,providing some guidance for future research.

Hydrogen-Assisted C-C Coupling on Reaction of CuC3H-Cluster Anion with CO

A fundamental study on C-C coupling,that is the crucial step in the Fischer-Tropsch synthesis(FTS)process to obtain multi-carbon products,is of great importance to tailor catalysts and then guide a more promising pathway.It has been demonstrated that the coupling of CO with the metal carbide can represent the early stage in the FTS process,while the related mechanism is elusive.Herein,the reactions of the CuC3H-and CuC3-cluster anions with CO have been studied by using mass spectrometry and theoretical calculations.The experimental results showed that the coupling of CO with the C3H-moiety of CuC3H can generate the exclusive ion product COC3H-.The reactivity and selectivity of this reaction of CuC3H-with CO are greatly higher than that of the reaction of CuC3-with CO,and this H-assisted C-C coupling process was rationalized by theoretical calculations.

A nickel-iron layered double hydroxide-supported Au catalyst for efficient electrocatalytic C-C coupling reaction coupled with H_(2) production

Coupling of cathodic H_(2) production with electrosynthesis of organic compounds not only solves the problem of sluggish oxygen evolution reaction(OER) kinetics, but also produces valuable chemicals. However, this strategy has rarely been explored for direct and selective C(sp~3)-H activation to construct C-C bonds, which could significantly enhance the synthetic efficiency in organic synthesis. Here, we report a nickel-iron layered double hydroxide-supported gold catalyst(Au/NiFe-LDH) for efficient electrocatalytic C-C coupling reaction in direct C(sp~3)-H alkynylation of tertiary aliphatic amines with 1-iodoalkynes, which is coupled with H_(2) production. Specifically, triethylamine and 1-iodoalkynes undergo efficient alkynylation to afford propargylamine in high yield(79%) and recycling ability without addition of external oxidants, coupling with 78-fold higher H_(2) productivity compared with water splitting under the same potential. This work may shed light on OER-substituted reaction towards C-C bond formation reactions under mild conditions.

Heterogeneous h-BN@Cyclodextrin@Pd（II） Nanomaterial： Fabrication, Characterization and Application as a Highly Efficient and Recyclable Catalyst for C-C Coupling Reactions

An efficient and ligand-free method for the Suzuki and Heck cross-coupling reactions has been success- fully developed using h-BN-supported palladium as the catalyst. This green methodology represents a cost-effective and operationally convenient process for the synthesis of biaryls, stilbenes and acrylates. Wide scope of substrates, good to excellent yields, low reaction time, water as solvent, ligand-free, non-toxicity and recyclability of the catalyst are the main merits of these protocols. In addition, the h-BN@y-CD@Pd（II） nanomaterial has been fully characte- rized by TG, SEM, IR, XRD, XPS and ICP-AES analysis. And it could be easily recovered and reused for at least nine times without any considerable loss of catalytic activity. Above all, this work demonstrates the possibility of using cyclodextrin-modified h-BN as an efficient support for the hydrophilic heterogeneous catalysts.

Comparison of the interface reaction behaviors of CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) solid-state systems based on the diffusion couple method

The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting process with vanadium slag.In this work,CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples were prepared and roasted for different time periods to illustrate and compare the diffusion reaction mechanisms.Then,the changes in the diffusion product and diffusion coefficient were investigated and calculated based on scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis.Results show that with the extension of the roasting time,the diffusion reaction gradually proceeds among the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples.The regional boundaries of calcium and vanadium are easily identifiable for the CaO–V_(2)O_(5) diffusion couple.Meanwhile,for the MnO_(2)–V_(2)O_(5) diffusion couple,MnO_(2) gradually decomposes to form Mn_(2)O_(3),and vanadium diffuses into the interior of Mn_(2)O_(3).Only a part of vanadium combines with manganese to form the diffusion production layer.CaV_(2)O_(6) and MnV_(2)O_(6) are the interfacial reaction products of the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples,respectively,whose thicknesses are 39.85 and 32.13μm when roasted for 16 h.After 16 h,both diffusion couples reach the reaction equilibrium due to the limitation of diffusion.The diffusion coefficient of the CaO–V_(2)O_(5) diffusion couple is higher than that of the MnO_(2)–V_(2)O_(5) diffusion couple for the same roasting time,and the diffusion reaction between vanadium and calcium is easier than that between vanadium and manganese.

Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.

Ligand assisted copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines

Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.

Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction of organoboronic acids with N-protected 4-iodophenyl alanine linked isoxazoles

Suzuki-Miyaura coupling reaction of N-protected 4-iodopheyl alanine isoxazoles with arylboronic acids,catalyzed by palladium,efficiently produce benzyl-N-（4-bipheyl）-2-（3-methyl-5（E）-2-aryl-1-ethenyl-4-isoxazolyl）-amino-2-oxoethyl）carba- mates in good yields.This process is first of its kind to construct carbon-carbon bond formation having biaryl motif on amino acid linked isoxazole moiety.

Pyroelectricity effect on photoactivating palladium nanoparticles in PbTiO3 for Suzuki coupling reaction

Combining microwave radiation with photocatalytic systems is a promising method to inhibit photogenerated electron-hole recombination and enhance the photocatalytic reaction performance. In this study, we have designed Pd/Pb TiO3 catalysts that can use both microwave fields and photocatalysis. Benefiting from the synergistic effect of microwave field and UV light, the Pb TiO3 crystals convert thermal energy into electrical energy via the pyroelectricity effect, generating positive and negative charges(q+ and q-), while Pd nanoparticles significantly improve the quantum efficiency of the photocatalytic process. The composite catalyst significantly enhances the reaction rate and selectivity of the model Suzuki coupling reaction performed with bromobenzene. Microwave fields can directly act on chemical systems, promoting or changing various chemical reactions in unique ways.

Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions

CuI/ethylene diamine/K2CO3/dioxane is shown to be a useful system for the cross coupling reactions of various aryl iodides and bromides with aryl and alkyl alkynes. Compared to the conventional Sonogashira reactions, the new procedure is free of palladium and phosphines.

The Application of Suzuki Coupling Reaction on the Preparation of Carbosilane Dendrimers with 4-(Naphthalen-1-yl)phenyl Core

Carbosilane dendrimers with p-bromophenyl core were synthesized by alternating Grignard and hydrosilylation reaction. And the α-naphthalenyl was connected to the core by the Suzuki coupling reaction. A new carbosilane dendrimer with big π-conjugated structure [4-（naphthalen-l-yl）phenyl core] was given. It shows Suzuki coupling reaction is an effective and powerful core-functionalization method and the satisfactory result can be obtained through prolonging the reaction time with the increase of the generation of dendrimer.

Light Inducing the Geometric Conversion of NiO_(6) to Trigger a Faster Oxygen Evolution Reaction Pathway:The Coupled Oxygen Evolution Mechanism

Developing highly active and robust oxygen evolution reaction(OER)electrocatalysts is still a critical challenge for water electrolyzers and metal-air batteries.Realizing the dynamic evolution of the intermediate and charge transfer during OER and developing a clear OER mechanism is crucial to design high-performance OER catalysts.Recently in Nature,Xue and colleagues revealed a new OER mechanism,coupled oxygen evolution mechanism(COM),which involves a switchable metal and oxygen redox under light irradiation in nickel oxyhydroxide-based materials.This newly developed mechanism requires a reversible geometric conversion between octahedron(NiO_(6))and square planar(NiO_(4))to achieve electronic states with both“metal redox”and“oxygen redox”during OER.The asymmetric structure endows NR-NiOOH with a nonoverlapping region between the dz^(2) orbitals and a_(1g)^(*)bands,which facilitate the geometric conversion and enact the COM pathway.As a result,NR-NiOOH exhibited better OER activity and stability than the traditional NiOOH.

CFD modeling of reaction and mass transfer through a single pellet: Catalytic oxidative coupling of methane

In this study a mathematical model of a small scale single pellet for the oxidative coupling of methane（OCM）over titanite pervoskite is developed.The method is based on a computational fluid dynamics（CFD）code which known as Fluent may be adopted to model the reactions that take place inside the porous catalyst pellet.The steady state single pellet model is coupled with a kinetic model and the intra-pellet concentration profiles of species are provided.Subsequent to achieving this goal,a nonlinear reaction network consisting of nine catalytic reactions and one gas phase reaction as an external program is successfully implemented to CFD-code as a reaction term in solving the equations.This study is based on the experimental design which is conducted in a differential reactor with a Sn/BaTiO3 catalyst（7-8 mesh） at atmospheric pressure,GHSV of 12000 h-1,ratio of methane to oxygen of 2,and three different temperatures of 1023,1048 and 1073 K.The modeling results such as selectivity and conversion at the pellet exit are in good agreement with the experimental data.Therefore,it is suggested that to achieve high yield in OCM process the modeling of the single pellet should be considered as the heart of catalytic fixed bed reactor.

An Efficient System TiCl_4-Al for the Homocoupling Reaction of Aromatic Aldehydes

The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols with high diasterepselectivities.