Boosting Electrochemical Nitrate Reduction at Low Concentrations Through Simultaneous Electronic States Regulation and Proton Provision.

Electrochemically converting nitrate (NO3 -) into ammonia (NH3) has emerged as an alternative strategy for NH3 production and effluent treatment. Nevertheless, the electroreduction of dilute NO3 - is still challenging due to the competitive adsorption between various aqueous species and NO3 -, and unfavorable water dissociation providing *H. Herein, a new tandem strategy is proposed to boost the electrochemical nitrate reduction reaction (NO3RR) performance of Cu nanoparticles supported on single Fe atoms dispersed N-doped carbon (Cu@Fe1-NC) at dilute NO3 - concentrations (≤100 ppm NO3 --N). The optimized Cu@Fe1-NC presents a FENH3 of 97.7% at -0.4 V versus RHE, and a significant NH3 yield of 1953.9 mmol h-1 gCu -1 at 100 ppm NO3 --N, a record-high activity for dilute NO3RR. The metal/carbon heterojunctions in Cu@Fe1-NC enable a spontaneous electron transfer from Cu to carbon substrate, resulting in electron-deficient Cu. As a result, the electron-deficient Cu facilitates the adsorption of NO3 - compared with the pristine Cu. The adjacent atomic Fe sites efficiently promote water dissociation, providing abundant *H for the hydrogenation of *NOx e at Cu sites. The synergistic effects between Cu and single Fe atom sites simultaneously decrease the energy barrier for NO3 - adsorption and hydrogenation, thereby enhancing the overall activity of NO3 - reduction.

Operando generated copper-based catalyst enabling efficient electrosynthesis of 2,5-bis(hydroxymethyl)furan.

Electrocatalytic upgrading of biomass-derived platform molecules has emerged as a sustainable and environmentally benign route to produce high-value chemicals. The main challenge lies in developing efficient catalysts for the selective activation of designated chemical bonds in the presence of various reducible groups. This work demonstrated a high-efficiency electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF), an important industrial synthetic reagent. A highly porous Cu-based catalyst was developed that achieved nearly 100% BHMF selectivity and long-term stability. Through comprehensive operando and ex-situ structural characterizations, an electrochemically generated catalyst with abundant Cu/Cu2O interfaces was identified as a catalytically active phase for HMF conversion. Deuterated BHMF, with the potential to produce deuterated drugs, was also synthesized using D2O as the deuterium source. Density functional theory calculations show that the Cu/Cu2O interface structure exhibits relatively low energy barriers for the hydrogenation of HMF to BHMF. This work provides insights into the origin of electrocatalytic hydrogenation activity and highlights the promising potential of the electrocatalytic synthesis of high-value chemicals.

Electrocatalytic Carbon Dioxide Reduction to Ethylene over Copper-based Catalytic Systems.

The electrocatalytic carbon dioxide (CO2 ) conversion to ethylene (C2 H4 ) has attracted significant attention in recent years. Copper-based catalytic systems have been proven to be the most efficient for producing C2 H4 from electrocatalytic CO2 reduction reaction. In this review, we present the recent progress on the electrocatalytic CO2 reduction to C2 H4 over copper-based catalytic systems, mainly focusing on reaction mechanism, design of catalysts and influences of electrolyte, CO2 supplement and electrolyzer on activity, selectivity and stability.

Insights into the Preparation of Copper Catalysts Supported on Layered Double Hydroxide Derived Mixed Oxides for Ethanol Dehydrogenation.

Acetaldehyde is an important chemical commodity and a building block for producing several other high-value products in the chemical industry. This has motivated the search for suitable, efficient, stable, and selective catalysts, as well as renewable raw materials such as ethanol. In this work, supported copper catalysts were prepared from CuZnAl layered double hydroxides (LDHs) with different copper contents (5, 10, and 20 wt %) for application in the ethanol dehydrogenation reaction (EDR). The samples were thoroughly characterized by a series of techniques, which allowed for analysis of all of the copper and zinc species involved in the different catalyst preparation steps and during the EDR. The results obtained by in situ quick extended X-ray absorption fine structure (EXAFS) measurements, combined with multivariate data analysis, showed that the copper content in the pristine LDH influenced the phase composition of the mixed oxide support, which consequently affected the dispersion of copper nanoparticles. The higher the copper content, the higher are the ZnAl2O4 and zinc tetrahedral prenuclei (TPN) contents, to the detriment of the ZnO content. All the samples showed high selectivity (>97%) and stability in the catalytic reactions at 300 and 350 °C, with no observed deactivation during 6 h on-stream. Although the samples with lower copper content presented higher copper dispersion and reactivity, the sample containing 20 wt % of copper outperformed the others, with greater conversion and higher activity toward acetaldehyde.

Easily Regenerated CuO/γ-Al2O3 for Persulfate-Based Catalytic Oxidation: Insights into the Deactivation and Regeneration Mechanism.

In this work, γ-Al2O3-supported CuO (c-CuO/Al2O3) materials are successfully synthesized using a novel impregnation-precipitation-decomposition method. The obtained c-CuO/Al2O3 catalyst shows excellent catalytic activities for bisphenol A (BPA) degradation with sodium persulfate (PDS) as an oxidant. Radical quenching tests and electron paramagnetic resonance (EPR) studies indicate that PDS activation is a combined mechanism involving both free radical and nonfree radical pathways. In a continuous large-scale degradation process, about 1.78 L of 20 ppm BPA can be completely removed within 480 min. Although c-CuO/Al2O3 can be deactivated after several reaction cycles, the catalytic activity can be regenerated after simple aerobic calcination. X-ray photoelectron spectroscopy (XPS) and Raman analysis confirm that the deactivation of c-CuO/Al2O3 should be attributed to the conversion of Cu(II) to Cu(I). The aerobic calcination could oxidize Cu(I) back to Cu(II), thus recovering the catalytic activity. In addition, the density functional technology (DFT) and temperature-programmed oxidation (TPD) results reveal that γ-Al2O3 can not only serve as a carrier to anchor the CuO particles but also can adsorb and activate PDS by introducing more basic sites on the surface. c-CuO/Al2O3 has high activity and can be regenerated easily, thus having great potential applications for wastewater treatment.

Copper-based catalyst from waste printed circuit boards for effective Fenton-like discoloration of Rhodamine B at neutral pH.

The carbonized waste printed circuit board (c-PCB) was used as novel copper-based catalyst for Fenton-like discoloration of Rhodamine B (RhB). The elemental ingredients, structure and morphology of the catalyst was investigated by multi-techniques. The catalytic activity of c-PCB for RhB discoloration was evaluated in the presence of H2O2, examining the factors of catalyst dosage, H2O2 dosage, solution pH, RhB concentration and temperature. RhB discoloration is improved with increasing catalyst dosage (0-2.0 g L-1), H2O2 dosage (0-0.15 mol L-1), solution pH (4.66-9.36) and temperature (30-50 °C). We found that c-PCB shows excellent catalytic activity for RhB discoloration in a broad pH range. RhB removal of 95.78% is obtained within 6 h at neutral pH (6.70). RhB discoloration is well described by the first-order kinetics, and the activation energy is calculated to be 87 kJ mol-1. The dominant role of OH radical in the c-PCB/H2O2 system is identified by quenching tests. The plausible pathway for RhB discoloration is discussed based on the time-dependent UV-vis spectra. The possible catalytic mechanism in the c-PCB/H2O2 system is also presented. Good reusability of c-PCB is verified by three cycles. This work opens a new strategy of "waste treating waste", facilitating management of hazardous solid wastes and cleaner treatment of textile wastewater.