Activity For Oxidation Reaction Research Articles

Selective hydroxylation of benzene via enhanced generation and utilization of hydroxyl radicals with CuZnSbO photocatalyst

Photocatalytic selective benzene hydroxylation via activation of C(sp2)–H under visible light remains a challenging reaction. Copper-incorporated mixed metal oxide photocatalysts have shown promise in addressing this difficulty by enabling visible light harvesting, controlled reactive oxygen species (ROS) generation, effective ROS utilization, and reactant adsorption. However, copper incorporated metal oxide catalysts were suffered from poor catalytic activity and selectivity due to leaching of Cu species. To solve this problem, herein, a novel stable mixed metal oxide (CuZnSbO) was prepared for the first time by applying a facile method. Copper introduction brought about the suitable band gap energy for a wide range of visible light harvesting of the CuZnSbO catalyst. The copper species play a key role in activating H2O2 to produce hydroxyl radicals (•OH) for benzene oxidation by controlling charge recombination. The mixed metal oxide of zinc and antimony supports the included copper strongly enabling copper stability. The CuZnSbO not only generates available hydroxyl radicals but also facilitates efficient hydroxyl radical consumption to initiate C(sp2)–H activation, forming benzene radical intermediates en route to phenol. That is ever reported. CuZnSbO delivered 31.51 % benzene conversion and 100 % phenol selectivity. This work demonstrates the promise of engineered mixed metal oxide that boosts Cu species utilization for H2O2 and benzene activation. The photocatalyst showed good activity in selective oxidative hydroxylation reactions through harnessing visible light and controlled ROS generation. Importantly, Cu cations govern the photocatalytic •OH generation mechanisms as shown by XPS and active site deactivation analysis.

Optimizing Hydrazine Activation on Dual‐Site Co‐Zn Catalysts for Direct Hydrazine‐Hydrogen Peroxide Fuel Cells

ABSTRACTDirect hydrazine‐hydrogen peroxide fuel cells (DHzHPFCs) offer unique advantages for air‐independent applications, but their commercialization is impeded by the lack of high‐performance and low‐cost catalysts. This study reports a novel dual‐site Co‐Zn catalyst designed to enhance the hydrazine oxidation reaction (HzOR) activity. Density functional theory calculations suggested that incorporating Zn into Co catalysts can weaken the binding strength of the crucial N2H3* intermediate, which limits the rate‐determining N2H3* desorption step. The synthesized p‐Co9Zn1 catalyst exhibited a remarkably low reaction potential of −0.15 V versus RHE at 10 mA cm−2, outperforming monometallic Co catalysts. Experimental and computational analyses revealed dual active sites at the Co/ZnO interface, which facilitate N2H3* desorption and subsequent N2H2* formation. A liquid N2H4‐H2O2 fuel cell with p‐Co9Zn1 catalyst achieved a high open circuit voltage of 1.916 V and a maximum power density of 195 mW cm−2, demonstrating the potential application of the dual‐site Co‐Zn catalyst. This rational design strategy of tuning the N2H3* binding energy through bimetallic interactions provides a pathway for developing efficient and economical non‐precious metal electrocatalysts for DHzHPFCs.

Greatly boosted H2O2 activity in two-electron water oxidation reaction on Zn-based catalysts by doping engineering

Electrocatalytic production of hydrogen peroxide (H2O2) by two electron water oxidation reaction (2e-WOR) is an environmental process with low cost and devoid of H2O2 storage and transportation. ZnO is one of the important promising 2e-WOR catalysts with relatively high activity and selectivity of H2O2. However, the active sites and the effects of oxygen defects of ZnO remain unknown, which hampers the further improvement in H2O2 formation. To explore the active sites and develop Zn-based catalysts with high performance, Ni, Cu and Co ions are chosen to form M0.1Zn0.9O (M = Ni, Cu and Co) catalysts. Combining the experimental results with density functional theory (DFT) calculations, the active site of 2e-WOR on Zn-based catalysts is first discovered to be the 3-coordinated surface Zn without surface oxygen defects since oxygen defects result in a strong interaction of ·OH with catalyst and then impede the 2e-WOR process. Catalysts with high activity and selectivity for 2e-WOR should have small nano-particle sizes without oxygen defects. Co0.1Zn0.9O is obtained with high activity (35.3 mmol min−1·gcat−1) and selectivity (82%) of H2O2 at 3.2 V vs RHE. This work provides valuable perspectives for designing and developing high-performing catalysts in 2e-WOR reaction.

Controlled synthesis of Mn\\M-doped NiP3/Cu3P (M=Cr, Ce, Bi and Co) as electrocatalysts for urea splitting reactions in alkaline solutions

Urea is generally used in agricultural fertilization to provide nutrients they need with the crops, however overuse of urea for fertilization can pollute the environment. Electrolysis urea is a greener way of treating urea, and in recent years electrolysis urea has been studied as a hot topic. It is mainly due to the fact that the potential of urea electrolysis is 0.37 V, which is smaller than the potential of traditional water splitting of 1.23 V. In this paper, a series of synthetic experiments were carried out by doping with the same content of Cr, Ce, Bi and Co into Mn-NiP3/Cu3P. It is found that Cr-doped Mn-NiP3/Cu3P possesses excellent electrochemical properties compared to nickel foam doped with the other three elements. At an iR compensation value of 70 %, Mn\\Cr-doped NiP3/Cu3P has strong catalytic activity and durability for urea oxidation reaction (UOR). At an ultra-low voltage of 1.352 V, the Mn\\Cr-doped NiP3/Cu3P catalyst had a catalytic current of 10 mA cm−2, a low Tafel slope (102.03 mV dec−1), a high Cdl (9.35 mF cm−2), and catalytic stability of more than 50 hours. The enhanced activity of Mn\\Cr-doped NiP3/Cu3P is attributed to rapid charge transfer, improved electrical conductivity, and increased electrochemical area. Density Functional Theory (DFT) calculations showed that synergic catalytic effect of Mn-Cr-NiP3 and Mn-Cr-Cu3P in the catalysts can effectively improve the adsorption capacity of the catalysts, this provides a new ideas of exploration for the electrolysis of urea with cheap and relatively low toxicity catalysts, which can effectively reduce the cost.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro‐Reforming Coupled with Hydrogen Production

Alkaline methanol‐water electrolysis system is regarded as an appealing strategy for electro‐reforming methanol into formate and producing hydrogen with low energy‐consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH‐, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm‐2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm‐2 for hydrogen evolution reaction (HER). Furthermore, membrane‐free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long‐term stability and FEs at high current density of 300 mA cm‐2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro-Reforming Coupled with Hydrogen Production.

Alkaline methanol-water electrolysis system is regarded as an appealing strategy for electro-reforming methanol into formate and producing hydrogen with low energy-consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH-, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm-2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm-2 for hydrogen evolution reaction (HER). Furthermore, membrane-free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long-term stability and FEs at high current density of 300 mA cm-2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Acid washing-assisted synthesis of porous Co3O4 nanosheet catalyst featuring efficient benzene oxidation performance

Co-based catalysts exhibit considerable catalytic activity in oxidative reactions, yet challenges remain in synthesizing Co3O4 materials featuring both large surface area and high activity. Here, ultrathin La0.029CoOx nanosheets were post-treated with various concentrations of dilute nitric acid to obtain the two-dimensionally geometric Co3O4-H nanosheets catalysts. Among them, the resultant Co3O4-0.1H catalyst disclosed significantly enhanced catalytic activity, enabling to achieve 100 % conversion of benzene at 230 °C under an ultrahigh weight hourly space velocity (WHSV) of 60,000 mL·g−1·h−1. Additionally, the catalyst also displayed excellent catalytic durability and well catalytic stability over 5 cyclic tests and 45 h of long-period operation. A thorough characterization results revealed that the superior catalytic performance of Co3O4-0.1H was attributed to its distinct nanosheet morphology, high specific surface area and abundant surface defect sites. This work highlights the effectiveness and simplicity of acid washing treatment strategy in improving the catalytic oxidation activity of transition metal oxide catalysts.

The Effect of Saccharin on SnNi Alloy: the Electrodeposition and its Electrocatalytic Activity in Ethanol Oxidation Reaction

The development of Direct Ethanol Fuel Cell (DEFC) has attracted much attention, as alternative energy sources due to its various advantages. However, among its various advantages, DEFC has several problems, such as the kinetics of the ethanol oxidation reaction. Transition metal-based catalysts such as nickel and tin are considered as potential catalysts for DEFC due to their oxophilic properties that can improve catalytic activity. In this study, the effect of saccharin on SnNi bimetallic alloy catalyst synthesized by electrodeposition method on copper wire substrate was investigated. SnNi samples were characterized by several techniques, including X-ray diffraction, Scanning electron microscopy, and energi dispersive X-ray spectrocopy. Saccharin addition had a significant effect on the morphology, crystallite size, and composition of the catalyst. The presence of saccharin causes the formation of more uniform particles and has a smaller size. The sample with the addition of saccharin had a smaller charge transfer resistance value 4.82 Ω, lower tafel slope by 115 mV/dec, and show higher jf/jb ratio by 0.55. Furthermore, as the current density decreases, the SnNi catalyst with saccharin has a slow decrease rate and higher stability than the SnNi catalyst without saccharin.

Aerobic Thiols Oxidative Coupling to Disulfides over Robust CoOx Nanoclusters Confined within Hierarchical Silicalite-1 Zeolite.

Disulfide is an important organic reagent and synthetic intermediate that is widely used in organic synthesis, polymers, and other fields, but its synthesis still suffers from many environmental pollution and economic problems. Here, we present an environmentally friendly and efficient base-free aerobic oxidative thiol coupling catalyzed by heterogeneous CoOx nanoclusters entrapped in hierarchical silicalite-1 zeolite, synthesized by combining silane pore expansion and metal coordination methods under hydrothermal conditions. It is confirmed that open hierarchical channels favor mass diffusion, and the chemical valence of Co species in CoOx/h-S-1-H is +2, which is different from that of Co3O4 particles in CoOx/h-S-1-I. CoOx nanoclusters, are strongly fixed in the channels of silicalite-1 zeolite via Co-O-Si bonds, which is of great importance for the high catalytic activity in both symmetrical and unsymmetrical oxidative thiol coupling reactions. After recycling experiments four times, the CoOx/h-S-1-H used has almost the same chemical state and the same distribution of Co(II) species as the fresh catalysts. Based on DFT calculations and inhibition experiments, the oxidative coupling of thiols undergoes a free radical mechanism in which Co(III) causes RS-H cleavage into RS· and H· species. Subsequently, two RS· radicals are coupled to disulfides, while H· radicals react with the O species to form H2O molecules. This work not only provides guidance on catalyst design and parameter optimization for oxidative thiol coupling but also advances the understanding of the aerobic oxidation mechanism.

Novel Gel method MXene-Supported Dual-Site PtNi-NiO for Electrocatalytic Water Reduction and Urea Oxidation.

Compared to the traditional oxygen evolution reaction (OER), the urea oxidation reaction (UOR) generally exhibits a lower overpotential during the electrolytic process, which is conducive to the hydrogen evolution reaction (HER) at the cathode. The superior structure and abundant sites play a crucial role in promoting the adsorption and cleavage of urea molecules. Therefore, this paper introduces a simple metal cation-induced gelation method to prepare an electrocatalyst with PtNi alloy-NiO dual sites supported on Ti3C2Tx, which simultaneously exhibits excellent UOR and HER performance. PtNi-NiOx/Ti3C2Tx demonstrates good catalytic activity for the urea oxidation reaction, requiring only 1.364V (overpotential of 0.994V) to achieve a current density of 100mAcm-2 in UOR, and also exhibits remarkable catalytic activity in the hydrogen evolution reaction, with PtNi-NiOx/Ti3C2Tx achieving a current density of 10mAcm-2 in HER with only 24mV of overpotential. In the UOR//HER two-electrode electrolysis cell, it requires only 1.361 and 1.538V to reach current densities of 10 and 100mAcm-2, respectively. According to density functional theory (DFT) calculations, the dual active sites can intelligently adsorb the electron-donating/electron-withdrawing groups in urea molecules, activate chemical bonds, and thereby initiate urea decomposition.

The trifunctional electrocatalytic activity of hierarchically structured porous carbon derived from environmentally malignant Prosopis juliflora

Finding an efficient and affordable multifunctional electrocatalyst with long-term durability has received paramount interest in the recent scenario. The present work attempted to facilitate ecologically threatful invasive biomass – P. juliflora- derived porous carbon as an effectual Pt support for trifunctional electrocatalytic applications. The preparation of Pt decorated P. juliflora -derived porous carbon (Pt/J-600, Pt/J-700, and Pt/J-800) involves simple hydrothermal carbonization, pyrolysis at various temperatures of 600, 700 & 800⁰C and polyol mediated reduction. The obtained XRD results reveal the turbostratic nature of the prepared porous carbon favoring to anchor the Pt NPs. Significantly, the estimated ID/IG ratios of Raman profile substantiates the highly defective structure of Pt/J-800. The TEM images disclose the agglomeration-free dispersion of Pt NPs in the Pt/J-800 electrocatalyst. The EIS analysis demonstrates the relatively low solution and charge transfer resistances (Rs = 0.646 Ω & Rct = 0.312 Ω). The desirable 4e- transfer with an improved limiting current density of -4.44 mA cm-2 signpost better oxygen reduction reaction (ORR) performance of Pt/J-800 than the other prepared electrocatalysts. Additionally, the high electrochemical surface area (652.72 m2 g-1) and good mass activity (49.09 mA mgpt-1) prove the excellent methanol oxidation reaction (MOR) activity. Moreover, a minimal overpotential of 31 mV @ 10 mA/cm2, and a lower Tafel slope of 32 mV/dec with 24 hr stable performance proved the efficient hydrogen evolution reaction (HER) performance of Pt/J-800. The remarkable electrochemical performance of Pt/J-800 is attributed to the enhanced surface area created by hierarchically porous carbon support and the uniform dispersion of Pt nanoparticles with optimum loading.

Revealing the mechanism of bifunctional PtLa electrocatalyst for highly efficient methanol oxidation, hydrogen evolution, and coupling reaction

The development of clean energy solutions, such as fuel cells and hydrogen energy, is crucial for addressing the global energy shortage. Platinum (Pt)-based catalysts are widely used in fuel cells and hydrogen energy generation (for example, via water electrolysis). However, reducing the amount of Pt used while maintaining the catalytic performance of such catalysts is essential. Herein, PtLa catalysts (PtxLay/C) doped with rare earth element lanthanum (La) with different Pt/La atomic ratios were synthesized using a simple chemical reduction method, resulting in Pt65La35/C, Pt78La22/C, Pt97La3/C, and Pt100/C. These PtxLay/C catalysts exhibited excellent electrocatalytic activity and stability in methanol oxidation reaction (MOR), hydrogen evolution reaction (HER), and their coupling reaction as MOR||HER under alkaline conditions. The mechanism by which La doping enhances the electrocatalytic properties and stability of Pt-based catalysts was investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), aberration-corrected scanning transmission electron microscopy (AC-STEM), in-situ Fourier transform infrared (FTIR) and operando Raman spectroscopy. For HER, La doping facilitated the adsorption and activation of H2O at Pt sites, improving water dissociation and *OH desorption and reducing Pt poisoning by *OH. This enhances both the catalytic performance and stability of PtxLay/C for HER. Pt78La22/C exhibited a considerably lower overpotential of only 111 mV at 100 mA cm−2 compared to commercial 20 wt% Pt/C (Pt/C-Johnson Matthey (JM)), which requires 153 mV. For MOR, La promotes CO bond cleavage and reduces CO adsorption at the Pt sites, thereby enhancing both the performance and stability of the catalysts. The mass activity (MA) of Pt78La22/C for MOR is 4.44 A mg−1Pt, which is 12.33 times higher than that of Pt/C-JM (0.36 A/mgPt), and surpasses those of Pt65La35/C, Pt97La3/C, and Pt100/C (2.93, 0.24, and 2.91 A mg−1Pt, respectively). Additionally, Pt78La22/C exhibited outstanding catalytic performance for MOR||HER, with a current density of 20 mA cm−2 at 1.030 V, demonstrating good stability with negligible voltage changes after a 15 h chronoamperometry (CA) testing. This study provides a new strategy for synthesizing Pt-based catalysts with enhanced efficiency and low-energy input for HER||MOR.

Immobilization of Metal Nanoparticles to an Ultrathin Two-Dimensional Conjugated Metal-Organic Framework for Synergistic Electrocatalysis.

Metal-organic frameworks (MOFs) have been considered as promising hosts for immobilizing ultrafine metal nanoparticles (MNPs) due to their high surface area and porosity. However, electrochemical applications of such emerging composites are severely limited by the poor electrical conductivity and large size of the MOFs. Herein, we report the general synthesis of incorporating various MNPs into a conjugated MOF ultrathin nanosheet (Cu-TCPP UNS) matrix, which not only prevents agglomeration and restricts the growth of MNPs but also benefits the exposure of active sites and the transport of electrons. Specifically, the obtained PtCu@Cu-TCPP UNSs exhibited nearly two times higher mass activity for the methanol oxidation reaction (MOR) than the commercial Pt/C catalyst. Mechanistic studies reveal that the strong interaction between MNPs and Cu-TCPP promotes the oxidation of the CO intermediate. Moreover, the PtCu@Cu-TCPP UNSs can be employed as bifunctional electrocatalysts to couple MOR with the hydrogen evolution reaction for highly efficient hydrogen production.

Bifunctional system constructed by NiCu-F/DSA electrode self-coupling for efficient removal of ammonia nitrogen from landfill leachate

ABSTRACT Landfill leachates containing high concentrations of ammonia nitrogen, due to its strong toxicity, large discharge and great environmental hazard, is in urgent need of efficient cleaning treatment. In this work, Ni1Cu0.25-F/DSA catalytic electrode was prepared via electrodeposition by means of fluorination-induced surface reconstruction. The surface of electrode was determined to be a porous sponge-like structure by physical characterizations. The electrode exhibited a superior ammonia oxidation reaction (AOR) activity and stability by a series of electrochemical tests. On this basis, a Ni1Cu0.25-F/DSA || Ni1Cu0.25-F/DSA bifunctional system was developed for efficient removal of ammonia nitrogen in landfill leachate. The results of denitrification experiment indicated that the removal efficiency of NH4 +-N and TN were 99.89% and 68.9%, respectively, when the electrolytic cell potential was 1.7 V, pH was 13 and the initial ammonia concentration was 600 mg L−1. The NH4 +-N removal efficiency remained above 95% after the cyclic denitrification experiment lasting for 6 days, which validates the robust stability of the electrode.

Empowering Tri-Functional Palladium's Catalytic Activity and Durability in Electrocatalytic Formic Acid Oxidation Reaction via Innovative Self-Caging and Alloying Strategies.

Direct formic acid fuel cells (DFAFCs) stand out for portable electronic devices owing to their ease of handling, abundant fuel availability, and high theoretical open circuit potential. However, the practical application of DFAFCs is hindered by the unsatisfactory performance of electrocatalysts for the sluggish anodic formic acid oxidation reaction (FAOR). Palladium (Pd) based nanomaterials have shown promise for FAOR due to their highly selective reaction mechanism, but maintaining high electrocatalytic durability remains challenging. In this study, a novel Pd-based electrocatalyst (UiO-Pd-E) is reported with exceptional durability and activity for FAOR, which can be attributed to the Pd nanoparticles encapsulated within a carbon framework where concurrent chemical alloying of Pd and Zr occurs. Further, the UiO-Pd-E demonstrates noteworthy multifunctionality in various electrochemical reactions including electrocatalytic ethanol oxidation reaction (EOR) and oxygen reduction reaction (ORR) in addition to the FAOR, highlighting its practical potentials.

Balanced adsorption and oxidation in a porous P, N-doped carbon prepared by melt-salt-mediated strategy for enhanced fenton-like reaction

The activation of persulfate oxidation processes using carbon-based catalysts is attractive for eliminating persistent aromatic organic pollutants in wastewater treatment. Herein, N and P co-doped carbonaceous (NPC) catalysts with an ultrahigh surface area were synthesized using a melt-salt-mediated strategy, employing Zeolitic Imidazolate Framework-8 as a self-sacrificing template. The NPC(1:1) carbon, prepared under optimized conditions, exhibited the highest surface area of 2001.5 m2/g, characterized by the highest number of defects and a high dispersion of N (1.89 %) and P (0.30 %) atoms on the carbon. This carbon catalyst exhibited a high capacity for adsorption and potential for activating persulfates in the removal of p-Nitrophenol (p-NP). Experimental data indicate a balance between adsorption and oxidation in the NPC(1:1)/PDS/p-NP system, with the highest catalytic removal rate achieved through moderate pre-adsorption of p-NP. Evidence from quenching, electron paramagnetic resonance (EPR), and amperometric i-t experiments suggests that the NPC(1:1)/PDS system primarily degrades p-NP through an electron transfer pathway. Defects in carbon and graphitic N were identified as catalytic sites. These defects resulted in an electron-deficient state, which leads to the activation of PDS and graphitic N was more reactive than both pyridinic and pyrrolic N in the adsorption of PDS molecules. Additionally, P-containing groups such as C-P-O, C-O-P, and C3-P were pinpointed as active sites on the carbons through DFT calculations. The intermediates during p-NP degradation were identified, and possible degradation pathways were proposed. A toxicity analysis indicated a significant reduction in overall toxicity following the oxidation treatment. This study provides innovative insights into the balance between adsorption and catalytic activity in porous carbon-activated persulfate oxidation reactions, thereby aiding in the development of enhanced oxidation catalysts for environmental remediation.

Investigation into geometric configurations and electronic properties of CeO2-supported gold clusters

A detailed understanding of the geometric structure and electronic properties of gold nanoparticles on the ceria surface is crucial for comprehending their unique catalytic activity. Using the first-principles method based on density functional theory, the adsorption of Aux (x = 1–4) clusters on the CeO2(111) surface was studied. It was discovered that the standing configurations of Au2 and Au3, as well as the tetrahedral structure of Au4, are the most stable adsorption structures. The stability of these configurations is jointly determined by the number and strength of Au-Au bonds, the Au-O bonding energy, and the interaction dynamics between the clusters and the substrate. The analysis of Bader charge, difference charge density and density of states suggested that lattice relaxation and electronic localization occur in the reduced Ce3+. The reduced amount and location of Ce3+ are significantly influenced by the position and charge transfer amount of Aux cluster. The adsorption of CO on Au4/CeO2(111) indicated that stronger Au-C bonding energy due to the hybridization of Au-5d and C-2p, thereby enhancing the catalytic activity for CO oxidation reactions.

Membrane‐Free Electrocatalytic Co‐Conversions of PBS Waste Plastics and Maleic Acid into High‐Purity Succinic Acid Solid

AbstractPlastic pollution, an increasingly serious global problem, can be addressed through the full lifecycle management of plastics, including plastics recycling as one of the most promising approaches. System design, catalyst development, and product separation are the keys in improving the economics of electrocatalytic plastics recycling. Here, a membrane‐free co‐production system was devised to produce succinic acid (SA) at both anode and cathode respectively by the co‐electrolysis of polybutylene succinate (PBS) waste plastics and biomass‐derived maleic acid (MA) for the first time. To this end, Cr3+‐Ni(OH)2 electrocatalyst featuring much enhanced 1,4‐butanediol (BDO) oxidation reaction (BOR) activity has been synthesized and the role of doped Cr has been revealed as an “electron puller” to accelerate the rate‐determining step (RDS) in the Ni2+/Ni3+ cycling. Impressively, an extra‐high SA production rate of 3.02 g h−1 and ultra‐high apparent Faraday efficiency towards SA (FEapparent=181.5 %) have been obtained. A carbon dioxide‐assisted sequential precipitation approach has been developed to produce high‐purity SA and byproduct NaHCO3 solids. Preliminary techno‐economic analysis demonstrates that the reported system is economically profitable and promising for future industrial applications.

Membrane-Free Electrocatalytic Co-Conversions of PBS Waste Plastics and Maleic Acid into High-PuritySuccinic Acid Solid.

Plastic pollution, an increasingly serious global problem, can be addressed through the full lifecycle management of plastics, including plastics recycling as one of the most promising approaches. System design, catalyst development, and product separation are the keys in improving the economics of electrocatalytic plastics recycling. Here, a membrane-free co-production system was devised to produce succinic acid (SA) at both anode and cathode respectively by the co-electrolysis of polybutylene succinate (PBS) waste plastics and biomass-derived maleic acid (MA) for the first time. To this end, Cr3+-Ni(OH)2 electrocatalyst featuring much enhanced 1,4-butanediol (BDO) oxidation reaction (BOR) activity has been synthesized and the role of doped Cr has been revealed as an "electron puller" to accelerate the rate-determining step (RDS) in the Ni2+/Ni3+ cycling. Impressively, an extra-high SA production rate of 3.02 g h-1 and ultra-high apparent Faraday efficiency towards SA (FEapparent=181.5%) have been obtained. A carbon dioxide-assisted sequential precipitation approach has been developed to produce high-purity SA and byproduct NaHCO3 solids. Preliminary techno-economic analysis demonstrates that the reported system is economically profitable and promising for future industrial applications.

Dual-doped medium-entropy phosphides for complete urea electrolysis

Developing dual-functional electrocatalysts for urea-water decomposition still faces significant challenges. In this study, the vanadium (V) and cerium (Ce) co-doped FeCoNi medium-entropy phosphide (VCe-FeCoNiP/NF) were effectively fabricated on nickel foam (NF) via “two-step method,” which involved hydrothermal treatment followed by phosphorization. Experimental results indicate that, benefiting from dual-ion doping and medium-entropy configuration, VCe-FeCoNiP/NF demonstrates unique electronic effects among the multimetallic elements, thereby exhibited remarkable catalytic activity for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). Under urea-water conditions (1 M KOH with 0.33 M urea), the VCe-FeCoNi/NF catalyst merely required 1.338 V (vs RHE) and an overpotential of 173 mV to attain a current density of 100 mA·cm−2 for UOR and HER, respectively. Moreover, it could stably operate at a current density of 20 mA·cm−2 for 225 h in overall urea-water decomposition. This work provides new insights for designing high-performance urea-water electrolysis catalysts.