Cu-based Catalysts Research Articles

Microenvironment Regulation, Promoting CO2 Conversion to Mono- and Multicarbon Products over Cu-Based Catalysts

Microenvironment Regulation, Promoting CO₂ Conversion to Mono- and Multicarbon Products over Cu-Based Catalysts

Fabrication of Cu-based catalysts for the synthesis of neopentyl glycol from hydroxypivalaldehyde hydrogenation: studies on the role of Zr promoter

Fabrication of Cu-based catalysts for the synthesis of neopentyl glycol from hydroxypivalaldehyde hydrogenation: studies on the role of Zr promoter

One-pot Hydrogenolysis of Polyethylene Terephthalate (PET) to p-xylene over CuZn/Al2O3 Catalyst.

Chemical upcycling of plastic wastes into valuable chemicals is a promising strategy for resolving plastic pollution, but economically viable methods currently are still lacking. Here, we report one-pot hydrogenolysis of PET plastic into p-xylene with an excellent yield (99.8 %) over a robust non-precious Cu-based catalyst, CuZn/Al2O3, in the absence of alcohol solvents. The presence of Zn species promotes the dispersion of Cu0 and increases the ratio of Cu+/Cu0, whereas the synergistic effect of Cu0 and Cu+ leads to a superior performance in the conversion of PET. The combination of GC-MS, 13C CP MAS NMR, 2D 1H-13C CP HETCOR NMR spectroscopy and kinetic studies for the first time demonstrates 4-methyl benzyl alcohol as an important reaction intermediate in the hydrogenolysis of PET. Mechanistic studies indicate that the conversion of PET mainly follows a hydrogenolysis process, involving the cleavage of ester bonds to alcohols and the C-O bond cleavage of alcohols to alkanes. This work not only brings new insight for understanding the upgrading pathway of PET, but also provides a guidance for the design of high-performance non-precious catalysts for the chemical upcycling of plastic wastes.

Enhanced H2S removal efficiency using CuO/Al2O3 catalyst impregnated with Ca(NO3)2: Influence of calcination temperature and mechanistic insights

A series of Ca(NO3)2-CuxO/Al2O3 catalysts with different calcination temperatures were designed to remove H2S effectively. Experimental and characterization results indicate that the calcination temperature can influence the catalyst's specific surface area, basic sites, and oxygen vacancies (VOs) concentration, thereby promoting its desulfurization performance. The Ca(NO3)2-CuxO/Al2O3 catalyst, calcined at 230 °C, exhibits an optimal surface structure. It demonstrates optimal H2S desulfurization performance at a temperature of 60 °C and relative humidity of 60 %, achieving a removal capacity of 486.67 mg/g. The VOs in CuxO (CuO and Cu2O) induce a unique catalytic of H2O, which generates hydroxy radicals (·OH) to oxidize the H2S anion to S. The introduction of Ca2+ provides basic sites to buffer pH, and NO3- with H+ removes H2S through cyclic oxidation, significantly enhancing the desulfurization performance of the Cu-based catalyst. The CaO-CuxO/Al2O3 catalyst, calcined at 700 °C, suffers from a deteriorated catalyst structure, leading to the rapid formation of desulfurization by-products due to the presence of CaO covering the catalyst surface. This diminishes the effectiveness of Cu, significantly impairing the catalyst's desulfurization performance (150.47 mg/g). Consequently, desulfurization mechanisms of Ca(NO3)2-CuxO/Al2O3 and CaO-CuxO/Al2O3 are proposed, offering effective strategies for the design and optimization of subsequent high-efficiency catalysts.

Selective CO2 Hydrogenation to Methanol by Halogen Deposition over a Cu-Based Catalyst

Selective CO₂ Hydrogenation to Methanol by Halogen Deposition over a Cu-Based Catalyst

Strategies and Mechanisms to Improve the Catalytic Performance of Cu-Based Catalyst for CO2 Electrochemical Reduction Reaction to Methane

This article introduces three significant ways of producing methane by electrocatalytic reduction of carbon dioxide. Electrocatalytic reduction of carbon dioxide can efficiently convert CO2 molecules into various high-energy fuels under ambient conditions. Methane gas, among them, stands out due to its relatively high calorific value, chemical stability, ease of storage and transportation. Therefore, research on electrocatalytic reduction of CO2 to generate methane is crucial. Common methods include adjusting catalyst morphology to expose more active sites, building nanoscale catalysts results in smaller-sized nanostructured copper and combining copper with other metals to form alloys, creating multi-metal catalysts. By optimizing these catalysts, we can efficiently reduce carbon dioxide into methane.

Harnessing the Potential of Machine Learning to Optimize the Activity of Cu-Based Dual Atom Catalysts for CO2 Reduction Reaction

Harnessing the Potential of Machine Learning to Optimize the Activity of Cu-Based Dual Atom Catalysts for CO₂ Reduction Reaction

Enhancing stability of industrial Cu-based catalysts under harsh reduction reaction conditions with silica armor protection

Cu-based catalysts are widely employed in various industrial processes, yet they are susceptible to deactivation due to sintering. Inhibiting the sintering deactivation of Cu nanoparticles has been a long-standing challenge for Cu-based catalysts. In this study, we propose a novel silica armor strategy to effectively protect Cu-based catalysts from sintering. Bioethanol dehydrogenation was selected as the test reaction, with the resulting products of acetaldehyde and hydrogen displaying strong reducing properties. After a 160-hour reaction period, the Cu nanoparticles in Cu/ZnO protected by a silica armor demonstrated exceptional stability, as the sintering of the Cu nanoparticles was effectively prevented. High resolution transmission electron microscope (HRTEM), X-ray absorption (XAS), and theoretical calculations were carried out to disclose the reasons for the stabilization of Cu nanoparticles by silica armor. The physical confinement created by the silica armor and the interactions between silicon species and Cu species efficiently suppressed the sintering of Cu particles. Furthermore, our research has showcased the potential application of the silica armor strategy on commercially available catalysts, highlighting its ability to effectively prevent the sintering of Cu particles on high-Cu content Cu/ZnO/Al2O3 industrial catalysts.

Recycling copper wire waste into active Cu-based catalysts for value-added chemicals production via CO2 electrochemical reduction

The CO2 electroreduction reaction (CO2RR) is a method for producing value-added compounds from CO2. This study aimed to use copper from wiring waste to create Cu-based catalysts on Vulcan XC-72R carbon for converting CO2 into valuable chemicals. Copper nanopowder with an average crystallite size of 27 nm derived from the wiring waste solution was utilized as the starting material for mono and bimetallic catalysts preparation. During the bimetallic PdCu/C catalyst synthesis, a galvanic displacement reaction between Pd and Cu occurred, resulting in the formation of PdCu alloy and a reduction in the copper crystallite size. The inclusion of Pd on Cu/C in CO2RR decreased the onset potentials for C1 and C2 chemical production. The yields of methanol, formic acid, and formaldehyde products were generally increased as the Pd:Cu ratio increased. The 1:2-PdCu/C exhibited the smallest crystallite size and an onset potential of less than −1.0 V, resulting in the highest Faradaic efficiency of the products. This catalyst converted CO2 into formic acid (FE = 71.5 %) at a potential of −0.8 V and methanol (FE = 65.4 %) at −0.5 V. The catalyst’s stability was demonstrated for more than 6000 s at current densities of approximately 2 mA mg-1catalyst.

In-situ fabrication of defect rich Cu2+1O on electrodeposited Cu cone arrays for promoting electrocatalytic anode hydrogen production

The low-potential formaldehyde oxidation reaction (FOR) is a significant replacement for oxygen evolution reaction, as FOR can couple with the cathode hydrogen evolution reaction (HER) to obtain a bipolar H2 production system with an extra low cell voltage. Cu-based electrocatalysts offer cost advantages in FOR but suffer from poor intrinsic activity and stability. Herein, a novel defect rich CF-Cu@Cu2+1O/Cu pinecone-shaped array electrocatalyst is fabricated by in-situ solution immersion of electrodeposited Cu cone arrays on foam for efficient and stable formaldehyde selective oxidation reaction to co-produce hydrogen and valuable formate. Benefitting from the partially mixed Cu2+1O in metallic copper and concomitant production of defect rich oxygen vacancies, only 0.04 VRHE is required for electrocatalytic FOR at 100 mA·cm−2 under alkaline conditions. FOR current density of CF-Cu@Cu2+1O/Cu electrode exhibits 2.35 times than that of CF-Cu (144 mA·cm−2) and 77 times than that of copper foam (4.4 mA·cm−2) at 0.5 VRHE. Moreover, the special pinecone-shaped structure is constructed to modify Cu-based catalysts with substantially enhanced stability. A FOR-HER co-electrolysis device of CF-Cu@Cu2+1O/Cu(+)||Pt/C(−) can achieve bipolar H2 production with an approaching 200 % Faradaic efficiency, requiring an extremely low electrical energy consumption of only ∼ 0.35 kWh per m3 of H2 and potential of 0.291 V at 100 mA·cm−2 at room temperature.

Fluorine-regulated Cu catalyst boosts electrochemical reduction of CO2 towards ethylene production

Electrochemical reduction of carbon dioxide (CO2RR) into value-added multi-carbon (C2) products utilizing renewable energy is a promising way to reduce carbon emission and achieve carbon neutrality. However, rational design of catalysts towards high C2 products selectivity remains a formidable task. Herein, fluorine modified copper catalyst was synthesised by thermal anneal in the presence of ammonium fluoride and sequential annealing in argon atmosphere. The charge distribution and coordination environment on copper surface were adjusted by doped fluorine atoms, which enables the formation of key intermediates and their sequential evolution into ethylene. The catalyst achieves a remarkable Faradaic efficiency (FE) of 40.6 % for eCO2RR to ethylene and remains stable over 13 hours. Density functional theory calculations indicates that the excellent CO2RR performance can be attributed to the suppressed hydrogen evolution on fluorine-doped copper catalyst. Our work brings a potential modification strategy of Cu-based catalyst for electrolytic CO2-to-C2 pathway.

Modulating charge transfer and constructing synergistic bimetallic active sites for CO-SCR reactions in inverse spinel

The selective catalytic reduction of NO by CO (CO-SCR) are frequently catalyzed by spinel due to its exceptional stability and redox capabilities. In this research, a ternary metal-based inverse spinel catalyst Cu0.67Mn0.33Fe2O4 was synthesized utilizing the glycerol self-templating technique. Some Fe3+ (Fe3+Td) sites are transferred to vacant octahedral sites through the occupancy of tetrahedral sites by Mn species. Mn3+ (Mn3+Td) sites synergistically interact with Cu2+ and Fe3+ ions on the octahedral sites to promote charge transfer, producing numerous oxygen-defective and highly mobile oxygen species and constructing Cu+-Ov-Fe2+ active sites on the surface. Various characterizations demonstrated that Cu+-Ov-Fe2+ has greater catalytic activity, resistance to alkali metals, and water toxicity than the Cu2+-Ov-Fe2+ active site of CuFe2O4. In situ DRIFTS further revealed the reaction mechanism of the ternary metal-based inverse spinel catalyst, and this study provides novel perspectives on the development of Cu-based catalysts for CO-SCR.

Membrane-Free Water Electrolysis for Hydrogen Generation with Low Cost.

Conventional water electrolysis relies on expensive membrane-electrode assemblies and sluggish oxygen evolution reaction (OER) at the anode. Here, we develop an innovative and efficient membrane-free water electrolysis system to overcome these two obstacles simultaneously. This system utilizes the thermodynamically more favorable urea oxidation reaction (UOR) to generate clean N2 over a new class of Cu-based catalyst (CuXO), fundamentally eliminating the explosion risk of H2 and O2 mixing while removing the need for membranes. Notably, this membrane-free electrolysis system exhibits the highest H2 Faradaic efficiency among reported membrane-free electrolysis work. In situ spectroscopic studies reveal that the new N2Hy intermediate-mediated UOR mechanism on the CuXO catalyst ensures its unique N2 selectivity and OER inertness. More importantly, an industrial-type membrane-free water electrolyser (MFE) based on this system successfully reduces electricity consumption to only 3.87 kWh Nm-3, significantly lower than the 5.17 kWh Nm-3 of commercial alkaline water electrolyzers (AWE). Comprehensive techno-economic analysis (TEA) suggests that the membrane-free design and reduced electricity input of the MFE plants reduce the green H2 production cost to US$1.81 kg-1, which is lower than those of grey H2 while meeting the technical target (US$2.00-2.50 kg-1) set by European Commission and United States Department of Energy.

Self-Assembled Controllable Cu-Based Perovskite/Calcium Oxide Hybrids with Strong Interfacial Interactions for Enhanced CH4 Electrosynthesis.

Cu-based perovskite oxide catalysts show promise for CO2 electromethanation, but suffer from unsatisfactory CH4 selectivity and poor stability. Here, we report self-assembled, controllable Cu-based perovskite/calcium oxide hybrids with strongly interacting interfaces for high-performance CH4 electrosynthesis. As proof-of-concept catalysts, the La2CuO4/(CaO)x (x from 0.2 to 1.2) series has tunable CaO phase concentrations and thus controllable interface sizes. The La2CuO4 and CaO components are intimately connected at the interface, leading to strong interfacial interactions mainly manifested by marked electron transfer from Ca2+ to Cu2+. In CH4 electrosynthesis, their activity and selectivity show a volcano-type dependence on the CaO phase concentrations and are positively correlated with the interface sizes. Among them, the La2CuO4/(CaO)0.8 delivers the optimal activity and selectivity for CH4, together with good stability, much better than those of a physical-mixture counterpart and most reported Cu-based perovskite oxides. Moreover, La2CuO4/(CaO)0.8 stands out as one of the most effective Cu-based catalysts for CH4 electrosynthesis, achieving a high CH4 selectivity of 77.6% at 300 mA cm-2. Our experiments and theoretical calculations highlight the significant role of self-assembly-induced strong interfacial interactions in promoting *CO adsorption/hydrogenation, intensifying resistance to structural degradation, and consequently underpinning the achievement of such optimized performance.

Investigation of a Hydrophobic Sputtered Cu Electrode to Electrocatalyze CO2 Towards a C2+ Product: The Effect of Substrate and Catalyst Thickness

The overuse of fossil fuels has resulted in massive CO2 emissions, causing global environmental problems. Renewable energy-driven electrocatalysis, which can convert CO2 into fuels and chemicals, is considered an emerging technology for carbon resource recycling. Cu-based catalysts sputtered on hydrophobic carbon paper and a polytetrafluoroethylene (PTFE) membrane were comparatively investigated, while the effect of the thickness of the Cu sputtering layer on the electrocatalytic CO2 reduction performance was investigated. Additionally, the effect of substrate properties on the distribution and morphology of sputtered Cu metal was investigated by SEM and XRD. With carbon paper as the substrate, the highest FEC2+ achieved was 70% at 200 mA/cm2, while the maximum value of FEC2+ on the Cu/PTFE electrode was realized with a Cu thickness of 400 nm (72%). Additionally, the PTFE substrate demonstrated a better inhibiting effect on HER, with a lower FEH2 and high FEC2+ over different applied current densities.

Oxidative Steam Reforming of Methanol over Cu-Based Catalysts

Several Cu and Ni-based catalysts were synthetized over Ce-based supports, either pure or mixed with different amounts of alumina (1:2 and 1:3 mol/mol). Different metal loadings (10–40 wt%) and preparation methods (wet impregnation, co-precipitation, and flame-spray pyrolysis—FSP) were compared for the oxidative steam reforming of methanol. Characterization of the catalysts has been performed, e.g., through XRD, BET, XPS, TPR, SEM, and EDX analyses. All the catalysts have been tested in a bench-scale continuous setup. The hydrogen yield and methanol conversion obtained have been correlated with the operating conditions, metal content, crystallinity of the catalyst particles, total surface area, and with the interaction of the metal with the support. A Cu loading of 20% wt/wt was optimal, while the presence of alumina was not beneficial, decreasing catalyst activity at low temperatures compared with catalysts supported on pure CeO2. Ni-based catalysts were a possible alternative, but the activity towards the methanation reaction at relatively high temperatures decreased inevitably the hydrogen yield. Durability and deactivation tests showed that the best-performing catalyst, 20% wt. Cu/CeO2 prepared through coprecipitation was stable for a long period of time. Full methanol conversion was achieved at 280 °C, and the highest yield of H2 was ca. 80% at 340 °C, higher than the literature data.

Dynamic Reconstruction of Cu Catalyst under Electrochemical NO Reduction to NH3.

The electrochemical reduction of nitric oxide (NO) to ammonia (NH3) offers a sustainable way of simultaneously treating the air pollutant and producing a useful chemical. Among catalyst candidates, Cu emerges as a stand-out choice for its superb NH3 selectivity and production rate. However, a comprehensive study concerning its catalytic behaviorin the NO reduction environment is lacking. Here, we unravel the dynamic rearrangement of Cu catalysts during NO reduction: the emergence of a bundled nanowire structure dependent on the applied potential. This unique structure is closely linked to an enhancement in double-layer capacitance, leading to a progressive increase in current density from 236 mA cm-2 by 20% over 1 h, while maintaining a Faradaic efficiency of 95% for NH3. Characterizations of Cu oxidation states suggest that the nanostructure results from the dissolution-redeposition of Cu in the aqueous electrolyte, influenced by the interaction with NO or other reactive intermediates. This understanding contributes to the broader exploration of Cu-based catalysts for sustainable and efficient NH3 synthesis from NO.

Enhancing CO2 Electroreduction Precision to Ethylene and Ethanol: The Role of Additional Boron Catalytic Sites in Cu-Based Tandem Catalysts.

The electrocatalytic conversion of carbon dioxide (CO2) into valuable multicarbon (C2+) compounds offers a promising approach to mitigate CO2 emissions and harness renewable energy. However, achieving precise selectivity for specific C2+ products, such as ethylene and ethanol, remains a formidable challenge. This study shows that incorporating elemental boron (B) into copper (Cu) catalysts provides additional adsorption sites for *CO intermediates, enhancing the selectivity of desirable C2+ products. Additionally, using a nickel single-atom catalyst (Ni-SAC) as a *CO source increases local *CO concentration and reduces the hydrogen evolution reaction. In situ experiments and density functional theory (DFT) calculations reveal that surface-bound boron units adsorb and convert *CO more efficiently, promoting ethylene production, while boron within the bulk phase of copper influences charge transfer, facilitating ethanol generation. In a neutral electrolyte, the bias current density for ethylene production using the B-O-Cu2@Ni-SAC0.05 hybrid catalyst exceeded 300 mA cm-2, and that for ethanol production with B-O-Cu5@Ni-SAC0.2 surpassed 250 mA cm-2. This study underscores that elemental doping in Cu-based catalysts not only alters charge and crystalline phase arrangements at Cu sites but also provides additional reduction sites for coupling reactions, enabling the efficient synthesis of distinct C2+ products.

Unconventional Electrocatalytic CO Conversion to C2 Products on Single-Atomic Pd-Agn Sites.

The electrochemical reduction of CO or CO2 into C2+ products has mostly been focused on Cu-based catalysts. Although Ag has also been predicted as a possible catalyst for the CO-to-C2+ conversion from the thermodynamic point of view, however, due to its weak CO binding strength, CO rapidly desorbs from the Ag surface rather than participates in deep reduction. In this work, we demonstrate that single-atomic Pd sites doped in Ag lattice can tune the CO adsorption behavior and promote the deep reduction of CO toward C2 products. The monodispersed Pd-Agn sites enable the CO adsorption with both Pd-atop (PdL) and Pd-Ag bridge (PdAgB) configurations, which can increase the CO coverage and reduce the C-C coupling energy barrier. Under room temperature and ambient pressure, the Pd1Ag10 alloy catalyst exhibited a total CO-to-C2 Faradaic efficiency of ~37 % at -0.83 V, with appreciable current densities and electrochemical stability, thus featuring unconventional non-Cu electrocatalytic CO-to-C2 conversion capability.

Role of electrons and H* in electrocatalytic nitrate reduction to ammonium for CuNi alloy

Electrocatalytic reduction of nitrate (NO3-) to ammonium (NH4+) is an environment friendly approach for treating nitrogen-containing wastewater. Consequently, electrocatalysts capable of effectively and selectively reducing NO3- to NH4+ receives growing attention. However, Cu-based catalysts demonstrate limited efficiency and the drawback of generating toxic NO2- though it is prevalent in the field of electrocatalytic reduction of NO3- (NO3RR). In this work, a CuNi alloy was synthesized on a Co foil through electrodeposition (marked as CuNi@Co) and its electrocatalytic performance for NO3RR was evaluated. XRD, EDS mapping and XPS characterization indicate CuNi exists with alloy state. Electrocatalytic experiments demonstrate that CuNi@Co exhibits an exceptional FENH3 of 99.12% at -0.64 V (vs. RHE). Importantly, no detrimental NO2- generated during NO3RR process because the reduction rate from NO2- to NH4+ is faster than that from NO3- to NO2-. Mechanistic analysis suggests that Cu serves as a ‘reservoir’ to provide electrons to facilitate the reduction of NO3- to NO2- during NO3RR process and the synergistic effect of Ni and Cu promotes more active hydrogen (H*) to participate the reduction process of NO2- to NH4+ not H2 generation, ultimately improving FENH3. This work elucidates the role of electrons and H* in electrocatalytic nitrate reduction to ammonium for CuNi alloy, providing new insights into the reduction process of NO3RR for Cu-based materials.