Cu-Based Materials for Enhanced C_(2+) Product Selectivity in Photo-/Electro-Catalytic CO_(2) Reduction: Challenges and Prospects

Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.

Fabrication of highly dispersed carbon doped Cu-based oxides as superior selective catalytic oxidation of ammonia catalysts via employing citric acid-modified carbon nanotubes doping CuAl-LDHs

In this work,the CuAl-LDO/c-CNTs catalyst was fabricated via in situ oriented assembly of layered-double hydroxides(LDHs)and citric acid-modified carbon nanotubes(c-CNTs)followed by annealing treatment,and evaluated in the selective catalytic oxidation(SCO)of NH_(3)to N_(2).The CuAl-LDO/c-CNTs catalyst presented better catalytic performance(98%NH_(3)conversion with nearly 90%N_(2)selectivity at 513 K)than other catalysts,such as CuAlO_(x)/CNTs,CuAlO_(x)/c-CNTs and CuAl-LDO/CNTs.Multiple characterizations were utilized to analyze the difference of physicochemical properties among four catalysts.XRD,TEM and XPS analyses manifested that CuO and Cu_(2)O nanoparticles dispersed well on the surface of the Cu Al-LDO/c-CNTs catalyst.Compared with other catalysts,larger specific surface area and better dispersion of CuAl-LDO/c-CNTs catalyst were conducive to the exposure of more active sites,thus improving the redox capacity of the active site and NH_(3)adsorption capacity.In-situ DRIFTS results revealed that the internal selective catalytic reduction(iSCR)mechanism was found over CuAl-LDO/c-CNTs catalyst.

The newly-assisted catalytic mechanism of surface hydroxyl species performed as the promoter in syngas-to-C2 species on the Cu-based bimetallic catalysts

In the conversion process of syngas-to-C_(2)species,the OH species are inevitably produced accompanying the production of key intermediates CH_(x)(x=1-3),traditionally,the function of surface OH species is generally accepted as the hydrogenating reactive species.This work for the first time proposed and confirmed the assisted catalytic mechanism of surface OH species that performed as the promoter for syngas-to-C_(2)species on Cu-based catalysts.DFT and microkinetic modeling results reveal that the produced OH species accompanying the intermediates CH_(x)production on the MCu(M=Co,Fe,Rh)catalysts can stably exist to form OH/MCu catalysts,on which the presence of surface OH species as the promoter not only presented better activity and selectivity toward CH_(x)(x=1-3)compared to MCu catalysts,but also significantly suppressed CH_(3)OH production,providing enough CH_(x)sources to favor the production of C_(2)hydrocarbons and oxygenates.Correspondingly,the electronic properties analysis revealed the essential relationship between the electronic feature of OH/MCu catalysts and catalytic performance,attributing to the unique electronic micro-environment of the catalysts under the interaction of surface OH species.This new mechanism is called as OH-assisted catalytic mechanism,which may be applied in the reaction systems related to the generation of OH species.

Accelerated prediction of Cu-based single-atom alloy catalysts for CO_(2) reduction by machine learning

Various strategies,including controls of morphology,oxidation state,defect,and doping,have been developed to improve the performance of Cu-based catalysts for CO_(2) reduction reaction(CO_(2)RR),generating a large amount of data.However,a unified understanding of underlying mechanism for further optimization is still lacking.In this work,combining first-principles calculations and machine learning(ML)techniques,we elucidate critical factors influencing the catalytic properties,taking Cu-based single atom alloys(SAAs)as examples.Our method relies on high-throughput calculations of 2669 CO adsorption configurations on 43 types of Cu-based SAAs with various surfaces.Extensive ML analyses reveal that low generalized coordination numbers and valence electron number are key features to determine catalytic performance.Applying our ML model with cross-group learning scheme,we demonstrate the model generalizes well between Cu-based SAAs with different alloying elements.Further,electronic structure calculations suggest surface negative center could enhance CO adsorption by back donating electrons to antibonding orbitals of CO.Finally,several SAAs,including PCu,AgCu,GaCu,ZnCu,SnCu,GeCu,InCu,and SiCu,are identified as promising CO_(2)RR catalysts.Our work provides a paradigm for the rational design and fast screening of SAAs for various electrocatalytic reactions.

Microstructure of Cu-based Amorphous Composite Coatings on AZ91D Magnesium Alloy by Laser Cladding

To improve the sliding wear resistance of AZ91D magnesium alloy, Cu-based amorphous composite coatings made of CuaTTi34Zr11Nis and Cu47Ti34Zr11Ni8＋20 wt pct SiC powders were fabricated on AZ91D magnesium alloy by laser cladding, respectively. SEM （scanning electron microscopy）, EDS （energy dispersive X-ray spectroscopy）, XRD （X-ray diffraction） and TEM （transmission electron microscopy） techniques were employed to study the phases of the coatings. The results show that the coatings mainly consist of amorphous phase and different intermetallic compounds. The reason of formation of amorphous phase and the function of SiC particles were explained in details.

Rational design strategies of Cu-based electrocatalysts for CO_(2) electroreduction to C_(2) products

Electrochemical reduction of CO_(2)(CO_(2)RR)to high value-added chemicals is an effective way to remove excess CO_(2) from the atmosphere.Due to the unique propensity of Cu for valuable hydrocarbons,Cu-based electrocatalysts are the most potential catalysts that allow the conversion of CO_(2) into a variety of C_(2) products such as ethylene and ethanol.Rational design of Cu-based catalysts can improve their directional selectivity to C_(2) products.Hence,in this review,we summarize the recent progress in the mechanistic studies of Cu-based catalysts on reducing CO_(2) to C_(2) products.We focus on three key strategies for efficiently enhancing electrocatalytic performance of Cu-based catalysts,including tuning electronic structure,surface structure,and coordination environment.The correlation between the structural characteristics of Cu-based catalysts and their activity and selectivity to C_(2) products is discussed.Finally,we discuss the challenges in the field of CO_(2) electroreduction to C_(2) products and provide the perspectives to design efficient Cu-based catalysts in the future.

Recent advances in Cu-based nanocomposite photocatalysts for CO_2 conversion to solar fuels

COconversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of COto useful solar fuels such as CO, CH, CHOH, and CHOH. Among studied formulations, Cubased photocatalysts are the most attractive for COconversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for COconversion, which includes metallic copper, copper alloy nanoparticles（NPs）, copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for COconversion with much-enhanced energy conversion efficiency and production rates.

Formation Mechanism of Curved Martensite Structures in Cu-based Shape Memory Alloys

The curved martensite structures have been observed in CuZnAI-based shape memory alloys by both transmission electron microscope and optical microscope. It was found that the curved martensite structures observed in as-solution treated, as-aged and as-trained alloys usually occurred around dislocation tangles or precipitate, at the plate boundary or grain boundary, and when the growing plates collided with each other or alternate mutually.

Cycle performance of Cu-based oxygen carrier based on a chemical-looping combustion process

The cycle life of oxygen carrier（OC） is crucial to the practical applications of chemical looping combustion（CLC）. Cycle performance of Cu/SiO2 prepared with a mechanical mixing method was evaluated based on a CLC process characterized with an added methane steam reforming step. The Cu/SiO2 exhibited high redox reactivity in the initial cycles, while the performance degraded with cycle number. Through characterization of the degraded Cu/SiO2, the performance degradation was mainly caused by the secondary particles＇ fragmentation and the fine particles＇ local agglomeration, which worsened the distribution and diffusion of the reactive gases in the packed bed. A regeneration method of the degraded OC based on re-granulation has been proposed, and its mechanism has been illustrated. With this method, the performance of the degraded OC through 420 redox cycles was recovered to a level close to the initial one.

Carbon Nano-tube Supported Cu-based Catalyst for Methanol Synthesis Developed by Xiamen University

The Chemistry and Chemical Engineering School of Xiamen University has successfully developed the multi-walled nanotube catalyst with small and uniform diameter and has mastered the corresponding technology for manufacture of carbon nanotube. It is learned that this technology has been for the first time developed inside ;and has reached the internationally advanced level with some indicators commanding a globally leading position.

Improved catalytic performance of CO_(2) electrochemical reduction reaction towards ethanol on chlorine-modified Cu-based electrocatalyst

Effective electrochemical conversion of CO_(2) to value-added liquid multi-carbon products driven by renewable energy is a promising approach to alleviate excessive CO_(2) emission and achieve large-scale renewable energy storage.However,the selectivity and catalytic activity towards liquid multi-carbon products of CO_(2) electroreduction reaction are still unsatisfactory due to the sluggish C-C coupling process and the formation of complex oxygen-containing intermediates.Hence,designing and fabricating highly effective electrocatalysts is crucial for practical applications in this field.Here,we developed Cl-modified Cu catalyst(Cu-Cl)for efficient electrochemical reduction of CO_(2) to ethanol.The optimal Faradaic efficiency and partial current density of ethanol on the Cu-Cl sample reached 26.2%and 343.2 mA·cm^(-2) at-0.74 V(vs.reversible hydrogen electrode(RHE)),which were 1.66 and 1.76 times higher than those of the catalyst without Cl decoration,outperforming those in most previously reported works.Density functional theory(DFT)calculations revealed that the Cl-modified Cu surface suppressed the parasitic hydrogen evolution reaction(HER)and reduced the energy barrier for the C-C coupling process,making the formation of key intermediates favorable for ethanol production.Thus,the decoration of Cl on the Cu surface facilitated ethanol formation.

Effect of cerium on wettability of mechanically milled Cu-based brazing alloy powder

CuSn powders and Till2 powders were milled using high energy mechanical milling to prepare Cu-based alloy powders for brazing diamond. And Ce was added to the milled Cu-based alloy powders to improve the wettability. It is found that the wetting angle reaches the minimum value 13.2° and the maximum spreading area 178 mm2 is achieved when the amount of Ce is 0.75 wt%. And Ce remarkably reduces the surface tension of liquid alloy, which improves the climbing height along the diamond and forms a massive support profile. And the results show that Ce can effectively improve the transverse rupture strength （TRS） due to high wettability. The wear characteristics of the diamonds brazed with Cu-based alloy containing 0.75 wt% Ce mainly consist of integrity, micro-fracture, fracture and rubdown, diamonds pull-out can not easily happen.

Structure design of high-performance Cu-based shape memory alloys

The effects of various structure factors on the properties(superelasticity mainly) of Cu-based shape memory alloys(SMAs) were systematically evaluated in this review article through literatures combining with our work. It is concluded that besides the decisive role of grain orientation, the grain boundary(GB) characteristics also play important roles in the superelasticity, which include GB area, GB type, GB morphology and GB direction in descending order of the effect significance. According to the above results, the prior principles of structure design are proposed for high-performance Cu-based SMAs from most to least important:(1) obtaining grain orientation with high phase transformation strain;(2) increasing grain size or reducing GB area;(3) obtaining straight low-energy GBs, especially low-angle GBs;(4) trying to make GB direction parallel to external stress. Consistent with the main or all principles, the bamboo-like-grained and columnar-grained(CG) Cu-based SMAs show excellent comprehensive properties.

Direct manufacturing of Cu-based alloy parts by selective laser melting

The frequent defects of the metal parts, such as non-fully melting, thermal strain, and balling, which are produced by selective laser melting （SLM） that is a novel method of one-step manufacturing, are analyzed theoretically and experimentally. The processing parameters significantly affect the quality of the final parts, and simultaneously, the appropriate laser mode and the special scanning strategy assure a satisfying quality of the final parts. The SLM experiment is carried out using Cu-based powder. The metal part is divided into several scanned regions, each of which is scanned twice at the cross direction with different scanning speeds. The microstructure is analyzed on microscope. The results show that the part is metallurgically bonded entity with a relative density of 95%, and the microstructure is composed of equiaxial crystal and dendritic crystal whose distributions are mainly decided by the scanning strategy.

Tribological properties of Cu-based composites with S-doped NbSe_2

In this study, S-doped NbSea （NbSo.aSel.8） powders were fabricated, and the corresponding Cu-based composites （Cu/NbSo.eSe1.8） were obtained by powder metallurgy technique. The phase compositions, physical, and tribological properties of Cu-based composites were investigated systematically. The results show that Cu matrix reacts with NbSo.2Sel.8 to produce Cu2Se and Cu0.38NbSo.2Se1.8 during sintering process, which influences the physical and tribological properties of Cu-based composites significantly. Specially, with NbS0.2Se1.8 content increasing, the density of Cu/ NbSo.2Se1.8 composites decreases, and the hardness increases firstly and then decreases, while the electric resistivity in- creases slightly. In addition, the incorporation of NbSo.2Se1.8 enhances the tribological properties of Cu greatly, which is attributed to the lubricating effect of Cuo,38NbSo.2Se1.8 and the reinforcement effect of Cu2Se. In particular, when the content of NbSo.2Sel.8 is 6 wt%, the Cu-based composite has the best tribological properties.

Effect of Milling Tools on the Microstructure and Property of Cu-Based Composites Prepared by Mechanical Alloying

Cu and Nb powders were used as starting materials to produce Cu-Nb and Cu-NbC-WC composites by mechanical alloying. X-ray diffraction, scanning electron microscopy, transmission electron microscopy observations and microhardness measurements have been used to study the effects of milling tools on the phase, microstructure and property of the composites. The results revealed that a single-phase nanocrystalline solid solution was obtained using stainless steel vials and balls （Alloy 1）. Nevertheless, Cu-7 wt% Nb powders milled by tungsten carbon vials and balls exhibited an amorphous phase （Alloy 2）. The as-milled powders were then vacuum hot-pressing sintered. The microstructure of sintered Alloy 1 consisted of Nb nanoparticles and Cu nanograins. Instead, Alloy 2 showed a microstructure with NbC nanoparticles and WC submicron-sized particles dispersed throughout the Cu matrix. Furthermore, Alloy 2 （～ 322 HV） had a higher microhardness than Alloy 1 （～ 302 HV）.

Regulation of the activity,selectivity,and durability of Cu-based electrocatalysts for CO_(2) reduction

CO_(2)electroreduction offers a promising approach to alleviate global warming and reduce petroleum consumption simultaneously,due to its capability to convert the greenhouse gas CO_(2)to valuable fuels and chemicals by using renewable electricity.Electrocatalyst has an essential impact on the CO_(2)electroreduction performance.Among the diverse exploited materials,Cu is the only monometallic electrocatalyst that can produce CO and hydrocarbons.However,its activity,selectivity,and durability are not satisfactory for practical applications.Here,we make a comprehensive survey of the recent progress in enhancing Cu-based electrocatalysts with the strategies such as oxidation pre-treatment,heteroatom doping,morphological control,and surface modification.This review provides an overview of the current status and future opportunities for Cu-catalyzed CO_(2)electroreduction.It may contribute to the rational design of Cu-based electrocatalysts with improved performance and thus advance practical CO_(2)electrolyzer development.

Realizing methanol synthesis from CO and water via the synergistic effect of Cu^(0)/Cu^(+)over Cu/ZrO_(2) catalyst

The optimizing utilization of ca rbon resources has drawn wide attention all over the world,while exploiting the high-efficiency catalytic routes remains a challenge.Here,a direct methanol synthesis route is realized from pure CO and H_(2)O over 10%Cu/t-ZrO_(2) catalyst,where the time yield of methanol is144.43 mmol mol_(Cu)^(-1)h^(-1)and the methanol selectivity in hydrocarbons is 100%,The Cu species highly dispersed in the t-ZrO_(2) support lead parts of them in the cationic state.The Cu^(+)sites contribute to the dissociation of H_(2)O,providing the H*source for methanol synthesis,while the formed Cu^(0) sites promote the absorption and transfer of H*during the reaction.Moreover,the H_(2)O is even a better H resource than H_(2) due to its better dissociation effectivity in this catalytic system.The present work offers a new approach for methanol synthesis from CO and new insight into the process of supplying H donor.

Strong metal-support interactions between highly dispersed Cu^(+) species and ceria via mix-MOF pyrolysis toward promoted water-gas shift reaction

The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF)structure.The obtained highly dispersed Cu/CeO_(2)-MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5μmolCOgcat^(-1).s^(-1)at 300℃and high stability of about 120 h.Based on comprehensive studies of electronic structure,pyrolysis strategy has significant effect on enhancing metal-support interaction and then stabilizing interfacial Cu^(+)species under reaction conditions.Abundant Cu^(+)species and generated oxygen vacancies over Cu/CeO_(2)-MOF catalyst played a key role in CO molecule activation and H2O molecule dissociation,respectively.Both collaborated closely and then promoted WGSR catalytic performance in comparison with traditio nal supported catalysts.This study shall offer a robust approach to harvest highly dispersed catalysts with finely-tuned metal-support interactions for stabilizing the most interfacial active metal species in diverse heterogeneous catalytic reactions.

THE FAILURE MECHANISM OF REVERSE SHAPE MEMORYEFFECT IN A Cu-BASE ALLOY

The interior structural evolution accompanying reverse shape memory effect (RSMEin a Cu-Zn-Al alloy was studied by means of transmission electron microscopy. It was found that RSME is closely related to bainitic transformation in this alloy during the isothermal reaction at moderate temperatures. At a given temperature and a certain external constraint stress, the shape memory effect depends mainly on the aging time.During the early stage, the shape memory effect enhances with the increase of reactiotn time. Then it will decrease gradually apon further aging. If the alloy is overaged, the stacking faults of bainite will disappear gradually by the motion of partial dislocations through which long range diffusion of solute atoms takes place, giving rise to the deterioration of RSME. When all the bainite transforms to α phase, RSME will lose completely.