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Nano bimetallic oxides as nanoproteases have the great advantages in the heterogeneous hydrolysis of proteins. Here, we report that bimetallic delafossite CuFeO2 submicron particles (CuFeO2 SMPs) display a high protease activity towards selective cleavage of peptide bond involving hydrophobic residue at 25 centidegree. CuFeO2 SMPs have excellent regeneration performance with high structural stability. The strong Lewis acidity of Fe(III) and the strong nucleophilicity of Cu(I) bound hydroxyl groups are both necessary for the high protease activity of CuFeO2 SMPs. Low-valent metal ion has a great advantage in that low-valent Cu(I) bound hydroxyl has strong nucleophilicity, resulting in promotion of protein hydrolysis via high-efficient bimetallic catalysis. This study provides evidence that the protease activity of CuFeO2 SMPs depends on metal ion-bound hydroxyls on their surface. Our findings highlight that the valence of metal ions in artificial protease and their surface hydroxyls are two important factors that determine their catalytic efficiency.

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The self-sufficient heterogeneous photo-Fenton (SH-PF) system was constructed for doxycycline hydrochloride (DOH) degradation with hydroxyapatite (Hap) modified CuFeO2 (Hap/CuFeO2) composites through H2O2 in-situ production. The modification of Hap could improve the specific surface area, visible-light response, light conversion efficiency, photoelectron lifetime and oxygen vacancies (OVs) of CuFeO2, which was conducive to H2O2 production and DOH degradation in SH-PF system. Notably, Hap/CuFeO2 fabricated with 0.5 g Hap (Hap/CuFeO2-0.5) displayed more superior performance for DOH degradation compared to other synthesized catalysts. The Hap/CuFeO2-0.5 load and initial solution pH for DOH degradation in SH-PF system were optimized, and the Hap/CuFeO2-0.5 had good reusability and stability. The •OH was the main active species for DOH degradation, and the facilitation effect of •O2- and photoelectrons on DOH degradation was associated with the H2O2 production in the present work. In addition, the capture of photogenerated holes suppressed the recombination of photogenerated carriers, elevating the production of photoelectrons and thereby enhancing H2O2 production and DOH degradation. The degradation pathways for DOH were proposed and the comprehensive toxicities of DOH were relieved after degradation in SH-PF system.

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Ammonia (NH3 ) is a promising hydrogen (H2 ) carrier for future carbon-free energy systems, due to its high hydrogen content and easiness to be liquefied. Inexpensive and efficient catalysts for ammonia electro-oxidation reaction (AOR) are desired in whole ammonia-based energy systems. In this work, ultrasmall delafossite (CuFeO2 ) polyhedrons with exposed high-index facets are prepared by a one-step NH3 -assisted hydrothermal method, serving as AOR pre-catalysts. The high-index CuFeO2 facet is revealed to facilitate surface reconstruction into active Cu-doped FeOOH nanolayers during AOR processes in ammonia alkaline solutions, which is driven by the favorable Cu leaching and terminates as the 2p levels of internal lattice oxygen change. The reconstructed heterostructures of CuFeO2 and Cu-doped FeOOH effectively activate the dehydrogenation steps of NH3 and exhibit a potential improvement of 260 mV for electrocatalytic AOR at 10 mA cm-2 compared to the pre-restructured phase. Further, density functional theory (DFT) calculations confirm that a lower energy barrier of the rate-determining step (*NH3 to *NH2 ) is presented on high-index CuFeO2 facets covered with Cu-doped FeOOH nanolayers. Innovatively, lattice oxygen atoms in Fe-based oxides and oxyhydroxide are involved in the dehydrogenation steps of AOR as a proton acceptor, broadening the horizons for rational designs of AOR catalysts.

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A novel Fenton-like catalyst made of reduced graphene oxide-coated CuFeO2 (rGO-coated CuFeO2) was synthesized by the hydrothermal reaction method to remove terramycin from aqueous solutions. The catalytic degradation performance of rGO-coated CuFeO2 for terramycin was verified with H2O2 activation. The characterization reveals that rGO-coated CuFeO2 has a micro- and mesoporous structure, with groups such as C=C/C-C, CH2-CO, and HO-C=O found on the surface. The Fenton-like catalytic degradation of terramycin by rGO-coated CuFeO2 was in line with the pseudo-second-order kinetic model, and the elevated temperature accelerated the reaction. Terramycin was catalytically degraded by rGO-coated CuFeO2 in two steps: terramycin was first adsorbed by rGO, and then Fenton-like degradation took place on its surface. This research presents new insight into the design and fabrication of Fenton-like catalysts with enhanced performance.

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Herein, an optoelectronic device synthesized from a CuFeO2/CuO/Cu nanocomposite was obtained through the direct combustion of Cu foil coated with Fe2O3 nanomaterials. The chemical, morphological, and optical properties of the nanocomposite were examined via different techniques, such as XRD, XPS, TEM, SEM, and UV/Vis spectrophotometer. The optical reflectance demonstrated a great enhancement in the CuFeO2 optical properties compared to CuO nanomaterials. Such enhancements were clearly distinguished through the bandgap values, which varied between 1.35 and 1.38 eV, respectively. The XRD and XPS analyses confirmed the chemical structure of the prepared materials. The produced current density (Jph) was studied in dark and light conditions, thereby confirming the obtained optoelectronic properties. The Jph dependency to monochromatic wavelength was also investigated. The Jph value was equal to 0.033 mA·cm-2 at 390 nm, which decreased to 0.031 mA·cm-2 at 508 nm, and then increased to 0.0315 mA·cm-2 at 636 nm. The light intensity effects were similarly inspected. The Jph values rose when the light intensities were augmented from 25 to 100 mW·cm-2 to reach 0.031 and 0.05 mA·cm-2, respectively. The photoresponsivity (R) and detectivity (D) values were found at 0.33 mA·W-1 and 7.36 × 1010 Jones at 390 nm. The produced values confirm the high light sensitivity of the prepared optoelectronic device in a broad optical region covering UV, Vis, and near IR, with high efficiency. Further works are currently being designed to develop a prototype of such an optoelectronic device so that it can be applied in industry.

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In Fenton or Fenton-like processes, the key step is to catalyze H2O2 and produce highly reactive OH radicals. More efforts are then focus on designing efficient heterogeneous Fenton catalysts by activating H2O2 to generate OH at the highest possible steady state concentration. In this study, using the antibiotic ofloxacin as target organic pollutant, we firstly demonstrate a point of view for improving OH utilization efficiency by regulating surface chemical reactions to minimizing its migration distance to the target pollutant. C doped g-C3N4 incorporated CuFeO2 (CCN/CuFeO2) exhibited almost ten times higher ofloxacin degradation rate constant than our previously reported CuFeO2 {012} catalyst (0.1634 vs 0.0179 min-1). Since similar amount of OH was generated, the different inhibition effect of tert-butyl alcohol and nitrobenzene on the ofloxacin degradation confirmed that the much-enhanced ofloxacin degradation was attributed to the surface Fenton reaction process. According to XPS and EXAFS characterization, the C-O-Cu bond between g-C3N4 and CuFeO2 established a closed-circuit surface Fenton reaction mechanism. H2O2 was adsorbed and decomposed into OH/O2- over ≡Cu + site in CuFeO2. The successful construction of CCN/CuFeO2 creates a negative surface potential and benefits the enrichment of target antibiotics from water, which greatly reduces the migration distance of OH/O2•- to adjacent pollutant and then increases the OH/O2- utilization efficiency by avoiding the unwanted quenching. Hence, CCN/CuFeO2 possesses superior Fenton catalytic activity and long-term stability.

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The two shortcomings of the Fenton-like catalyst delafossite-type oxide (CuFeO2) lie in its spontaneous agglomeration and deactivation under neutral working pH. To remedy these drawbacks, novel Fenton-like catalyst chitosan-derived maillard reaction productions coated CuFeO2 with abundant oxygen vacancies (OV-CuFeO2@MRPs) was synthesized by hydrothermal method with no extra chemical reducing agent. The systemic characterization illustrated that richer oxygen vacancies and higher particles dispersion of OV-CuFeO2@MRPs contributed to better Rhodamine B (RhB) degradation under neutral pH compared to pure CuFeO2. Cooper antisite defects in OV-CuFeO2@MRPs were evidenced by X-ray powder diffraction (XRD), fourier transform infrared spectrometer (FTIR), Raman spectra and energy dispersive X-ray spectrometer (EDX) linescan. To keep the charge balance, OV-CuFeO2@MRPs should form rich oxygen vacancies, which was confirmed by X-ray photoelectron spectroscopy (XPS) and solid-state electron paramagnetic resonance spectrometer (solid-state EPR). Furthermore, the electrochemical impedance spectroscopy (EIS) analysis revealed that oxygen vacancies could improve the electron transfer. Scavenging experiments and electron spin resonance spectroscopy (ESR) analysis demonstrated that OH was main active radical during Fenton-like reaction, and the density functional theory (DFT) calculation verified that the oxygen vacancy could effectively adsorb H2O2 and elongate O-O bond of H2O2, thus promoting the activation of H2O2 into OH.

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Mass transfer efficiency and catalytic reactivity are the two major hurdles for heterogeneous catalytic wet peroxide oxidation (CWPO) technologies. To address these issues, nanocomposite CuFeO2/Al2O3 was synthesized and assessed as a novel catalyst for enhanced adsorption and oxidation of anionic pollutants (catechol and reactive red 195 (RR195)) in waters. With a positive charge on the nanocomposite by introducing Al2O3, the adsorption of anionic pollutants was promoted. The surface complexation reaction on CuFeO2/Al2O3, which fits well to the Langmuir isotherm, has engined the mass transfer of pollutants to the nanocatalyst that demonstrated 96.46% and 99.75% removal of catechol and RR195 at pH 3, respectively. CuFeO2/Al2O3 also showed good performance in various reaction media including binary pollutants system and real wastewaters. The hydroxyl radical in aqueous solution played a major role in the pollutants degradation. The CWPO, which followed the Haber-Weiss mechanism, has been accelerated by the Cu and Fe redox cycles. The robustness of the catalyst was verified by negligible amount of metal leaching from the catalysts along with stable catalytic performance after five cycles. Upon the observed results, CuFeO2/Al2O3 with the synergistic effect has shown to be a promising catalyst for removal and degradation of anionic pollutants in CWPO.

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The visible-light induced heterogeneous photo-Fenton-like (HPF-like) process is regarded as a promising technique for organic pollutants degradation due to its efficient utilization of solar energy and high H2O2 activation activity. This study prepared the CuFeO2/biochar catalysts via hydrothermal technique at no extra reductant and systematically investigated their band structure and photoelectric properties. The dispersed distribution of CuFeO2 particles in CuFeO2/biochar composites narrowed bandgap of CuFeO2 and promoted electron transport of CuFeO2. Compared with CuFeO2, the CuFeO2/biochar containing 1.0 g biochar in the preparation (CuFeO2/biochar-1.0) possessed higher carrier density and longer photoelectron lifetime, which is beneficial to higher catalytic performance. The apparent rate constant for tetracycline as target pollutant degradation by CuFeO2/biochar-1.0 was 2.0 times higher than that by CuFeO2. The acquired optimum conditions for tetracycline degradation were 220 mg L-1 CuFeO2/BC-1.0, 22 mM H2O2 and pH 6.4 using response surface methodology. The quenching experiments and ESR analysis revealed that OH was the predominant active species, and photoelectron and O2- were auxiliary species. The photoelectron could promote in-situ recycling of Cu2+ to Cu+ and Fe3+ to Fe2+, which significantly improved H2O2 activation by CuFeO2. The possible pathway of tetracycline was proposed according to intermediates identified by HPLC/MS. The toxicity analysis demonstrated that the overall toxicity of the identified intermediates was reduced in HPF-like system.

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Herein, we report a simple approach to synthesize CuFeO2/TNNTs photocathodes composed of high-temperature resistance n-type Nb-doped TiO2 nanotube arrays (TNNTs) and p-type CuFeO2 for CO2 reduction. TNNTs were prepared by anodic oxidation on TiNb alloy sheets and CuFeO2/TNNTs were then prepared by coating precursor liquid onto TNNTs followed by heat treatment in argon atmosphere. The microstructures of CuFeO2/TNNTs and TNNTs before and after heat treatment were investigated by SEM and TEM. The phase compositions of CuFeO2/TNNTs were studied by XRD and XPS, and the light absorption performance were tested by UV-vis diffuse reflectance spectrum. Results show that TNNTs exhibit a regular nanotube arrays structure and this structure is well remained after the calcination at 650 °C. In addition, TNNTs show similar semiconductor properties to n-type TiO2, which enables them to be integrated with p-type CuFeO2 to obtain composite photocathodes with a p-n junction. The synthesized CuFeO2/TNNTs photocathode is well crystallized because no other crystalline iron or copper compounds are included in the prepared photocathode. Furthermore, the photocathode shows high light absorption and fast carrier transport due to the appropriate band gap and p-n junction. As a result, high photoelectrocatalytic CO2 reduction performance with high selectivity to ethanol is obtained on this photocathode.

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The regular architecture (n-i-p) of perovskite solar cells (PSCs) has attracted increasing interest in the renewable energy field, owing to high certified efficiencies in the recent years. However, there are still serious obstacles of PSCs associated with spiro-OMeTAD hole transport material (HTM), such as (i) prohibitively expensive material cost (∼150-500 $/g) and (ii) operational instability at elevated temperatures and high humidity levels. Herein, we have reported the highly photo, thermal, and moisture-stable and cost-effective PSCs employing inorganic CuFeO2 delafossite nanoparticles as a HTM layer, for the first time. By exhibiting superior hole mobility and additive-free nature, the best-performing cell achieved a power conversion efficiency (PCE) of 15.6% with a negligible hysteresis. Despite exhibiting a lower PCE as compared to the spiro-OMeTAD-based control cell (19.1%), nonencapsulated CuFeO2-based cells maintained above 85% of their initial efficiency, while the PCE of control cells dropped to ∼10% under continuous illumination at maximum power point tracking after 1000 h. More importantly, the performance of control cells was quickly degraded at above 70 °C, whereas CuFeO2-based cells, retaining ∼80% of their initial efficiency after 200 h, were highly stable even at 85 °C in ambient air under dark conditions. Besides showing significant improvement in stability against light soaking and thermal stress, CuFeO2-based cells exhibited superior shelf stability even at 80 ± 5% relative humidity and retained over 90% of their initial PCE. Overall, we strongly believe that this study highlights the potential of inorganic HTMs for the commercial deployment of long-term stable and low-cost PSCs.

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CuFeO2/CeO2 as a novel catalyst was synthesized and its catalytic performance was evaluated for electro-Fenton degradation of acid orange 7 (AO7). It was demonstrated from the characterization results that the rhombohedral structure of CuFeO2 and face-centered cubic fluorite structure of CeO2 remained stable after nanocomposite construction. The impact of such operating parameters as pH, current intensity and, catalyst amount was investigated and the optimum conditions (100 mgL-1 AO7, pH 3, 150 mgL-1 CuFeO2/CeO2, I: 150 mA) determination led to 99.3% AO7 removal and 79.1% COD removal in 60 min. The introduction of CeO2 as non-inert support had a significant impact on H2O2 electro-generation as an important step in AO7 removal. CuFeO2/CeO2 presented negligible metal leaching (iron 4.13%, copper 2.4%, and cerium 0.33%) which could be due to the strong interaction between active species and support. The nanocomposite performed efficiently in salty systems and two samples of real wastewaters due to Brønsted acidity character of ceria, which makes it a potential choice in industrial applications. The good performance of nanocomposite could be the result of the synergistic effect between Fe, Cu, and Ce. Regarding scavenging measurements results, the electro-Fenton process followed the Haber-Weiss mechanism. The by-products detection was performed using GC-MS analysis to propose an acceptable pathway for EF degradation of AO7. The BMG kinetics model (1/b = 0.969 (min) and 1/m = 0.269 (min-1)) was matched with the experimental data and described the kinetics of reaction very well. The catalytic activity of CuFeO2/CeO2 almost remained after six cycles. Based on the obtained results, CuFeO2/CeO2 using the benefit of the synergistic effect of Ce3+ with Fe2+ and Cu+can be introduced as a promising novel catalyst for the electro-Fenton reaction in wastewater treatment.

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Efficient sunlight-driven water-splitting devices can be achieved by using an optically and energetically well-matched pair of photoelectrodes in a tandem configuration. The key for maximizing the photoelectrochemical efficiency is the use of a highly transparent front photoelectrode with a band gap below 2.0 eV. Herein, we propose two-dimensional (2D) photonic crystal (PC) structures consisting of a CuFeO2-decorated microsphere monolayer, which serve as self-light-harvesting architectures allowing for amplified light absorption and high transparency. The photocurrent densities are evaluated for three CuFeO2 2D PC-based photoelectrodes with microspheres of different sizes. The optical analysis confirmed the presence of a photonic stop band that generates slow light and at the same time amplifies the absorption of light. The 410 nm sized CuFeO2-decorated microsphere 2D PC photocathode shows an exceptionally high visible light transmittance of 76.4% and a relatively high photocurrent of 0.2 mA cm-2 at 0.6 V vs a reversible hydrogen electrode. The effect of the microsphere size on the carrier collection efficiency was analyzed by in situ conductive atomic force microscopy observation under illumination. Our novel synthetic method to produce self-light-harvesting nanostructures provides a promising approach for the effective use of solar energy by highly transparent photocathodes.

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Bimetallic oxide CuFeO2 as a new heterogeneous catalyst has shown much higher catalytic ability for activating peroxide than single-metal oxides. The present work demonstrated a synergistic microwave (MW) enhanced Fenton-like process with CuFeO2 for rapid decolorization of azo dye Orange G (OG). The MW irradiation dramatically enhanced the OG degradation efficiency, achieving 99.9% decolorization within 15min at pH5. The XRD analysis of reused CuFeO2, together with metal leaching tests, indicated merits of recycling for CuFeO2. The subsequent surface element analysis by XPS for fresh and used CuFeO2 showed a complex network for reactions between copper-iron redox pairs and surface hydroxyl groups, leading to a synergistic Fenton-like system accelerated by MW irradiation. In the CuFeO2 initiated Fenton-like reactions, several oxidant species (i.e., OH, O2-, electron hole, and FeIVO) responsible to the OG oxidation were identified by quenching experiments, showing the MW generated high temperature and "hot spots" enhanced the yield of OH by generation of electron-hole pairs. Further, the 26 detected degradation products confirmed the OH dominant oxidation of OG. This study shows that the MW-enhanced Fenton-like reaction using CuFeO2 has potential applications for rapid decolorization of dye effluent.

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Microscaled CuFeO2 particles (micro-CuFeO2) were rapidly prepared via a microwave-assisted hydrothermal method and characterized by scanning electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy. It was found that the micro-CuFeO2 was of pure phase and a rhombohedral structure with size in the range of 2.8±0.6µm. The micro-CuFeO2 efficiently catalyzed the activation of peroxymonosulfate (PMS) to generate sulfate radicals (SO4-), causing the fast degradation of carbamazepine (CBZ). The catalytic activity of micro-CuFeO2 was observed to be 6.9 and 25.3 times that of micro-Cu2O and micro-Fe2O3, respectively. The enhanced activity of micro-CuFeO2 for the activation of PMS was confirmed to be attributed to synergistic effect of surface bonded Cu(I) and Fe(III). Sulfate radical was the primary radical species responsible for the CBZ degradation. As a microscaled catalyst, micro-CuFeO2 can be easily recovered by gravity settlement and exhibited improved catalytic stability compared with micro-Cu2O during five successive degradation cycles. Oxidative degradation of CBZ by the couple of PMS/CuFeO2 was effective in the studied actual aqueous environmental systems.

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In this study we present a new, environmental friendly and economic method, called Lt-delafossite process to treat industrial wastewater (initial Cu(2+)-concentrations of 1-15.6 g/l) by subsequent synthesis of nano-crystalline (doped) delafossite (CuFeO2) solely by precipitation and ageing at temperatures between 50 °C and 90 °C. The reached water purification rates are exclusively ≥99.99% for both wastewater models and wastewaters from electroplating industry. We succeeded to synthesize a mixture of 3R and 2H delafossite at 50 °C after 90 h and ≥70 °C after 16 h of ageing directly from industrial wastewater without any additional phases. In all cases green rust (GR), a Fe(II-III) layered double hydroxysulphate, Cu2O (cuprite) and Fe10O14(OH)2 (ferrihydrite) precipitates first. During ageing of the residues the metastable phases transform to delafossite. The residues are characterized by XRD, FTIR, SEM, TEM, VFTB and Mößbauer measurements.

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A new electrodeposition route was developed to prepare p-type CuFeO2 as a thin film-type electrode for use as a photocathode in a solar water splitting cell. The resulting p-CuFeO2 film has a bandgap energy of ca. 1.55 eV, with its conduction band edge located at a more negative potential than the reduction potential of water. Various photoelectrochemical properties of the p-CuFeO2 electrode were investigated, and its photoelectrochemical hydrogen production in 1 M NaOH solution was confirmed by gas chromatography. The incident photon-to-current conversion efficiency plot confirmed that p-CuFeO2 has the ability to utilize the entire range of visible light.