A method for using the residual energy in waste Li-ion batteries by regulating potential with the aid of overvoltage response.

The value of considerable residual energy in waste Li-ion batteries (WLIBs) is always neglected. At present, "this energy" is always wasted during the discharge process of WLIBs. However, if this energy could be reused, it would not only save a lot of energy but also avoid the discharge step of recycling of WLIBs. Unfortunately, the instability of WLIBs potential is a challenge to efficient utilization of this residual energy. Here, we propose a method that could regulate the cathode potential and current of the battery by simply adjusting the solution pH to utilize 35.08%, 88.4%, and 84.7% of the residual energy for removing heavy metal ions from wastewater, removing Cr (VI) from wastewater, and recovering copper from the solution, respectively. By taking advantage of the high internal resistance R of WLIBs and the sudden change of battery current I caused by iron passivation on the positive electrode of the battery, this method could induce the response of overvoltage η (η = IR) inside the battery at different pH levels to regulate the cathode potential µ of the battery to the three intervals. The potential ranges of the battery cathode corresponding to pH < 3.4, pH ≈ 3.4, and pH > 4 were µ > -0.47V, -0.47V < µ < -0.82V, and µ < -0.82V, respectively. This study provides a promising way and theoretical basis for the development of technologies for reusing residual energy in WLIBs.

Pd1Cu Single-Atom Alloys for High-Current-Density and Durable NO-to-NH3 Electroreduction.

Electrochemical reduction of NO to NH3 (NORR) offers a prospective method for efficient NH3 electrosynthesis. Herein, we first design single-atom Pd-alloyed Cu (Pd1Cu) as an efficient and robust NORR catalyst at industrial-level current densities (>0.2 A cm-2). Operando spectroscopic characterizations and theoretical computations unveil that Pd1 strongly electronically couples its adjacent two Cu atoms (Pd1Cu2) to enhance the NO activation while promoting the NO-to-NH3 protonation energetics and suppressing the competitive hydrogen evolution. Consequently, the flow cell assembled with Pd1Cu exhibits an unprecedented NH3 yield rate of 1341.3 µmol h-1 cm-2 and NH3-Faradaic efficiency of 85.5% at an industrial-level current density of 210.3 mA cm-2, together with an excellent long-term durability for 200 h of electrolysis, representing one of the highest NORR performances on record.

A comparative study of electrochemical reduction of levulinic acid on various electrodes in organic solvents.

Studies on the electrochemical hydrogenation (ECH) of levulinic acid (LA) to valeric acid (VA) or γ-valerolactone (GVL) have mainly focused on the electroreduction of LA in acidic aqueous solutions. However, the narrow range of applied potentials has hindered understanding of some mechanistic aspects of LA electrochemical conversion. Earlier, we discovered that employing proton-deficient non-aqueous reaction media provides more comprehensive insights into the mechanism of LA electrochemical reduction. Here, we conducted further investigations into the LA electroreduction process using cyclic voltammetry in various organic solvents on a Pt electrode and on various electrode materials in acetonitrile, both with and without the addition of proton donors. The products of the ECH processes were identified using HPLC. The solvent nature, the presence of proton donors, the electrode material, and the applied potential strongly influence the LA electroreduction process. This study reveals that LA, in the presence proton donors, can undergo electroreduction through different pathways, depending on the difference (ΔE1/2) between the reduction half-wave potential of protons and LA. When the difference is large, the LA reduction is incomplete and the formation of GVL is observed. Under the close reduction potentials of protons and LA, LA can be completely reduced to VA.

Self-Tandem Electrocatalytic NO Reduction to NH3 on a W Single-Atom Catalyst.

We design single-atom W confined in MoO3-x amorphous nanosheets (W1/MoO3-x) comprising W1-O5 motifs as a highly active and durable NORR catalyst. Theoretical and operando spectroscopic investigations reveal the dual functions of W1-O5 motifs to (1) facilitate the activation and protonation of NO molecules and (2) promote H2O dissociation while suppressing *H dimerization to increase the proton supply, eventually resulting in a self-tandem NORR mechanism of W1/MoO3-x to greatly accelerate the protonation energetics of the NO-to-NH3 pathway. As a result, W1/MoO3-x exhibits the highest NH3-Faradaic efficiency of 91.2% and NH3 yield rate of 308.6 µmol h-1 cm-2, surpassing that of most previously reported NORR catalysts.

Ultrathin Nitrogen-Doped Carbon Encapsulated Ni Nanoparticles for Highly Efficient Electrochemical CO2 Reduction and Aqueous Zn-CO2 Batteries.

Electrochemical CO2 reduction reaction (CO2 RR), powered by renewable electricity, has attracted great attention for producing high value-added fuels and chemicals, as well as feasibly mitigating CO2 emission problem. Here, this work reports a facile hard template strategy to prepare the Ni@N-C catalyst with core-shell structure, where nickel nanoparticles (Ni NPs) are encapsulated by thin nitrogen-doped carbon shells (N-C shells). The Ni@N-C catalyst has demonstrated a promising industrial current density of 236.7 mA cm-2 with the superb FECO of 97% at -1.1 V versus RHE. Moreover, Ni@N-C can drive the reversible Zn-CO2 battery with the largest power density of 1.64 mW cm-2 , and endure a tough cycling durability. These excellent performances are ascribed to the synergistic effect of Ni@N-C that Ni NPs can regulate the electronic microenvironment of N-doped carbon shells, which favor to enhance the CO2 adsorption capacity and the electron transfer capacity. Density functional theory calculations prove that the binding configuration of N-C located on the top of Ni slabs (Top-Ni@N-C) is the most thermodynamically stable and possess a lowest thermodynamic barrier for the formation of COOH* and the desorption of CO. This work may pioneer a new method on seeking high-efficiency and worthwhile electrocatalysts for CO2 RR and Zn-CO2 battery.

Electrochemical Dechlorination of Municipal Wastewater Effluent.

The use of sodium bisulfite as an electron donor to quench chloramine disinfectant residuals in municipal wastewater effluents prior to discharge incurs the cost of purchasing and transporting bisulfite to the utility and increases the loading of salts to the receiving water. In this study, degradation of chloramine residuals within authentic municipal wastewater effluents was achieved within a 30 min timescale using a reductive electrochemical reactor, which supplied electrons via a stainless-steel cathode under galvanostatic conditions without an ion exchange membrane separating the cathode and anode. Application of a 0.26 mA/cm2 cathodic current density reduced chloramines to ammonia and avoided oxidation at the IrO2-coated titanium anode of chloride to chlorine or chlorate and of ammonia to nitrite or nitrate. Net chloramine production was observed at a higher current density (2 mA/cm2). Chloramine degradation rates and Coulombic efficiencies were highest and electrical energy per order (EEO) values were lowest for the 304-grade stainless-steel cathode, which contains the highest nickel content, and for a stainless-steel cathode with a high surface area. Differences in ionic strength and pH were less important. For chloraminated municipal wastewater samples, the highest Coulombic efficiency was 4.1% and the lowest EEO value was 0.08 kWh/m3. An initial comparison indicated that the electricity cost associated with this EEO value would be comparable to the cost of sodium bisulfite for areas with low electricity costs.

Insights into Electrochemical Dehalogenation by Non-Noble Metal Single-Atom Cobalt with High Efficiency and Low Energy Consumption.

It is critical to discover a non-noble metal catalyst with high catalytic activity capable of replacing palladium in electrochemical reduction. In this work, a highly efficient single-atom Co-N/C catalyst was synthesized with metal-organic frameworks (MOFs) as a precursor for electrochemical dehalogenation. X-ray absorption spectroscopy (XAS) revealed that Co-N/C exhibited a Co-N4 configuration, which had more active sites and a faster charge-transfer rate and thus enabled the efficient removal of florfenicol (FLO) at a wide pH, achieving a rate constant 3.5 and 2.1 times that of N/C and commercial Pd/C, respectively. The defluorination and dechlorination efficiencies were 67.6 and 95.6%, respectively, with extremely low Co leaching (6 µg L-1), low energy consumption (22.7 kWh kg-1), and high turnover frequency (TOF) (0.0350 min-1), demonstrating excellent dehalogenation performance. Spiking experiments and density functional theory (DFT) verified that Co-N4 was the active site and had the lowest energy barrier for forming atomic hydrogen (H*) (ΔGH*). Capture experiments, electron paramagnetic resonance (EPR), electrochemical tests, and in situ Fourier transform infrared (FTIR) proved that H* and direct electron transfer were responsible for dehalogenation. Toxicity assessment indicated that FLO toxicity decreased significantly after dehalogenation. This work develops a non-noble metal catalyst with broad application prospects in electrocatalytic dehalogenation.

Electroreductive Defluorination of Unsaturated PFAS by a Quaternary Ammonium Surfactant-Modified Cathode via Direct Cathodic Reduction.

Remediation of per- and polyfluoroalkyl substances (PFAS) in groundwater remains a technological challenge due to the trace concentrations of PFAS and the strength of their C-F bonds. This study investigated an electroreductive system with a quaternary ammonium surfactant-modified cathode for degrading (E)-perfluoro(4-methylpent-2-enoic acid) (PFMeUPA) at a low cathodic potential. A removal efficiency of 99.81% and defluorination efficiency of 78.67% were achieved under -1.6 V (vs Ag/AgCl) at the cathode modified by octadecyltrimethylammonium bromide (OTAB). The overall degradation procedure started with the adsorption of PFMeUPA onto the modified cathode. This adsorption process was promoted by hydrophobic and electrostatic interactions between the surfactants and PFMeUPA, of which the binding percentage, binding mode, and binding energy were determined via molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The step-wise degradation pathway of PFMeUPA, including reductive defluorination and hydrogenation, was derived. Meanwhile, C-F bond breaking with direct electron transfer only was achieved for the first time in this study, which also showed that the C═C bond structure of PFAS facilitates the C-F cleavage. Overall, this study highlights the crucial role of quaternary ammonium surfactants in electron transfer and electrocatalytic activities in the electroreductive system and provides insights into novel remediation approaches on PFAS-contaminated groundwater.

Bacterial DNA Recognition by SERS Active Plasma-Coupled Nanogold.

It is shown that surface-enhanced Raman spectroscopy (SERS) can identify bacteria based on their genomic DNA composition, acting as a "sample-distinguishing marker". Successful spectral differentiation of bacterial species was accomplished with nanogold aggregates synthesized through single-step plasma reduction of the ionic gold-containing vapored precursor. A high enhancement factor (EF = 107) in truncated coupled plasmonic particulates allowed SERS-probing at nanogram sample quantities. Simulations confirmed the occurrence of the strongest electric field confinement within nanometric gaps between gold dimers/chains from where the molecular fingerprints of bacterial DNA fragments gained photon scattering enhancement. The most prominent Raman modes linked to fundamental base-pair molecular vibrations were deconvoluted and used to proceed with nitrogenous base content estimation. The genomic composition (percentage of guanine-cytosine and adenine-thymine) was successfully validated by third-generation sequencing using nanopore technology, further proving that the SERS technique can be employed to swiftly specify bioentities by the discriminative principal-component statistical approach.

Chemical and Electrochemical Reductions of Monoiminoacenaphthenes.

Redox properties of monoiminoacenaphthenes (MIANs) were studied using various electrochemical techniques. The potential values obtained were used for calculating the electrochemical gap value and corresponding frontier orbital difference energy. The first-peak-potential reduction of the MIANs was performed. As a result of controlled potential electrolysis, two-electron one-proton addition products were obtained. Additionally, the MIANs were exposed to one-electron chemical reduction by sodium and NaBH4. Structures of three new sodium complexes, three products of electrochemical reduction, and one product of the reduction by NaBH4 were studied using single-crystal X-ray diffraction. The MIANs reduced electrochemically by NaBH4 represent salts, in which the protonated MIAN skeleton acts as an anion and Bu4N+ or Na+ as a cation. In the case of sodium complexes, the anion radicals of MIANs are coordinated with sodium cations into tetranuclear complexes. The photophysical and electrochemical properties of all reduced MIAN products, as well as neutral forms, were studied both experimentally and quantum-chemically.

Electrochemical Behavior of ß-Cyclodextrin-Ni-MOF-74/Reduced Graphene Oxide Sensors for the Ultrasensitive Detection of Rutin.

Rutin, as a biological flavonoid glycoside, has very important medicinal value. The accurate and rapid detection of rutin is of great significance. Herein, an ultrasensitive electrochemical rutin sensor based on ß-cyclodextrin metal-organic framework/reduced graphene oxide (ß-CD-Ni-MOF-74/rGO) was constructed. The obtained ß-CD-Ni-MOF-74 was characterized by X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and nitrogen adsorption and desorption. The ß-CD-Ni-MOF-74/rGO presented good electrochemical properties benefiting from the large specific surface area and good adsorption enrichment effect of ß-CD-Ni-MOF-74 and the good conductivity of rGO. Under optimal conditions for the detection of rutin, the ß-CD-Ni-MOF-74/rGO/GCE showed a wider linear range (0.06-1.0 µM) and lower detection limit (LOD, 0.68 nM, (S/N = 3)). Furthermore, the sensor shows good accuracy and stability for the detection of rutin in actual samples.

Synthesis of α-Chloroarylacetic Acid via Electrochemical Carboxylation of α,α-Dichloroarylmethane Derivatives.

The electrocarboxylation of α,α-dichloroarylmethane derivatives in the presence of CO2 was achieved, providing several α-chloroarylacetic acid derivatives with modest yields but high selectivity (chlorinated vs. non-chlorinated or dicarboxylic acid products). The obtained products were then involved in several chemical transformations, underlining their potential as versatile intermediates in synthetic chemistry. A mechanism was also proposed based upon a control experiment and cyclic voltammetry (CV) study.

Strategies to Enhance CO2 Electrochemical Reduction from Reactive Carbon Solutions.

CO2 electrochemical reduction (CO2 ER) from (bi)carbonate feed presents an opportunity to efficiently couple this process to alkaline-based carbon capture systems. Likewise, while this method of reducing CO2 currently lags behind CO2 gas-fed electrolysers in certain performance metrics, it offers a significant improvement in CO2 utilization which makes the method worth exploring. This paper presents two simple modifications to a bicarbonate-fed CO2 ER system that enhance the selectivity towards CO. Specifically, a modified hydrophilic cathode with Ag catalyst loaded through electrodeposition and the addition of dodecyltrimethylammonium bromide (DTAB), a low-cost surfactant, to the catholyte enabled the system to achieve a FECO of 85% and 73% at 100 and 200 mA·cm-2, respectively. The modifications were tested in 4 h long experiments where DTAB helped maintain FECO stable even when the pH of the catholyte became more alkaline, and it improved the CO2 utilization compared to a system without DTAB.

Enhancing Electrochemical Nitrate Reduction to Ammonia over Cu Nanosheets via Facet Tandem Catalysis.

Electrochemical conversion of nitrate (NO3 - ) into ammonia (NH3 ) represents a potential way for achieving carbon-free NH3 production while balancing the nitrogen cycle. Herein we report a high-performance Cu nanosheets catalyst which delivers a NH3 partial current density of 665 mA cm-2 and NH3 yield rate of 1.41 mmol h-1 cm-2 in a flow cell at -0.59 V vs. reversible hydrogen electrode. The catalyst showed a high stability for 700 h with NH3 Faradaic efficiency of ≈88 % at 365 mA cm-2 . In situ spectroscopy results verify that Cu nanosheets are in situ derived from the as-prepared CuO nanosheets under electrochemical NO3 - reduction reaction conditions. Electrochemical measurements and density functional theory calculations indicate that the high performance is attributed to the tandem interaction of Cu(100) and Cu(111) facets. The NO2 - generated on the Cu(100) facets is subsequently hydrogenated on the Cu(111) facets, thus the tandem catalysis promotes the crucial hydrogenation of *NO to *NOH for NH3 production.

Tuning C1 /C2 Selectivity of CO2 Electrochemical Reduction over in-Situ Evolved CuO/SnO2 Heterostructure.

Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO2 electrochemical reduction (CO2 ER), are prone to undergo structure reconstruction under working conditions, thus bringing challenges to understanding the reaction mechanism and rationally designing catalysts. Herein, we for the first time elucidate the structural reconstruction of CuO/SnO2 under electrochemical potentials and reveal the intrinsic relationship between CO2 ER product selectivity and the in situ evolved heterostructures. At -0.85 VRHE , the CuO/SnO2 evolves to Cu2 O/SnO2 with high selectivity to HCOOH (Faradaic efficiency of 54.81 %). Mostly interestingly, it is reconstructed to Cu/SnO2-x at -1.05 VRHE with significantly improved Faradaic efficiency to ethanol of 39.8 %. In situ Raman spectra and density functional theory (DFT) calculations reveal that the synergetic absorption of *COOH and *CHOCO intermediates at the interface of Cu/SnO2-x favors the formation of *CO and decreases the energy barrier of C-C coupling, leading to high selectivity to ethanol.

Manipulating Electrocatalytic Activity of Perovskite Oxide Through Electrochemical Treatment.

Perovskite oxides are widely used in electrochemical cells, profiting from their excellent accommodation of different elements and structure stability. Here, it is reported that when rapidly exceeding the electrochemical stability window of a perovskite oxide through electrochemical treatment, nanoparticles can dynamically exsolve from the perovskite lattice, yielding a nanoparticle decorated material (NDM) with fascinating particle population and distribution. It is reported that as compared to the NDM produced by chemical gas reduction, electrochemical treatment fabricated NDM shows much better electrochemical performance. At 900 °C, a peak power density (PPD) of 896 mW cm-2 (more than tenfold enhancement) is obtained for a yttrium stabilized zirconia (YSZ) electrolyte-supported symmetrical cell with La0.43 Ca0.37 Ti0.8 Co0.1 Fe0.1 O3- δ (LCTCF) electrode after electrochemical treatment for several minutes, while it only reaches to 210 mW cm-2 after chemical gas treatment for tens of hours using humidified hydrogen as fuel. The study establishes a new fairyland for tuning the performance of-but not limited to-the electrochemical cells.

A Robust Approach to In Situ Exsolve Highly Dispersed and Stable Electrocatalysts.

Catalysts made of in situ exsolved metal nanoparticles often demonstrate promising activity and high stability in many applications. However, the traditional approach is limited by perovskites as prevailing precursor and requires high temperature typically above 900 K. Here, with the guidance of theoretical calculation, an unprecedented and substantially facile technique is demonstrated for Cu nanoparticles exsolved from interstitially Cu cations doped nickel-based hydroxide, which is accomplished swiftly at room temperature and results in metal nanoparticles with a quasi-uniform size of 4 nm, delivering an exceptional CO faradaic efficiency of 95.6% for the electrochemical reduction of CO2 with a notable durability. This design principle is further proven to be generally applicable to other metals and foregrounded for guiding the development of advanced catalytic materials.

Tailoring the Surface and Interface Structures of Copper-Based Catalysts for Electrochemical Reduction of CO2 to Ethylene and Ethanol.

Electrochemical CO2 reduction to valuable ethylene and ethanol offers a promising strategy to lower CO2 emissions while storing renewable electricity. Cu-based catalysts have shown the potential for CO2 -to-ethylene/ethanol conversion, but still suffer from low activity and selectivity. Herein, the effects of surface and interface structures in Cu-based catalysts for CO2 -to-ethylene/ethanol production are systematically discussed. Both reactions involve three crucial steps: formation of CO intermediate, CC coupling, and hydrodeoxygenation of C2 intermediates. For ethylene, the key step is CC coupling, which can be enhanced by tailoring the surface structures of catalyst such as step sites on facets, Cu0 /Cuδ+ species and nanopores, as well as the optimized molecule-catalyst and electrolyte-catalyst interfaces further promoting the higher ethylene production. While the controllable hydrodeoxygenation of C2 intermediate is important for ethanol, which can be achieved by tuning the stability of oxygenate intermediates through the metallic cluster induced special atomic configuration and bimetallic synergy induced the double active sites on catalyst surface. Additionally, constraining CO coverage by the complex-catalyst interface and stabilizing CO bond by N-doped carbon/Cu interface can also enhance the ethanol selectivity. The structure-performance relationships will provide the guidance for the design of Cu-based catalysts for highly efficient reduction of CO2 .

Direct Electron Transfer Coordinated by Oxygen Vacancies Boosts Selective Nitrate Reduction to N2 on a Co-CuOx Electroactive Filter.

Atomic hydrogen (H*) is used as an important mediator for electrochemical nitrate reduction; however, the Faradaic efficiency (FE) and selective reduction to N2 are likely compromised due to the side reactions (e.g., ammonia generation and hydrogen evolution reactions). This work reports a Co-CuOx electrochemical filter with CoOx nanoclusters rooted on vertically aligned CuOx nanowalls for selective nitrate reduction to N2, utilizing the direct electron transfer between oxygen vacancies and nitrate to suppress the contribution by H*. At a cathodic potential of -1.1 V (vs Ag/AgCl), the Co-CuOx filter showed 95.2% nitrate removal and 96.0% N2 selectivity at an influent nitrate concentration of 20 N-mg L-1. Meanwhile, the energy consumption and FE were 0.60 kW h m-3 and 53.5%, respectively, at a permeate flux of 60 L m-2 h-1. The presence of abundant oxygen vacancies on Co-CuOx was due to the change in the electron density of the Cu atom and a decrease of the coordination numbers of Cu-O via cobalt doping. Theoretical calculations and electrochemical tests showed that the oxygen vacancies coordinated nitrate adsorption and subsequent reduction reactions, thus suppressing the contribution of H* to nitrate reduction and leading to a thermodynamically favorable process to N2 via direct electron transfer.

Electrochemical Reduction of Halogenated Alkanes and Alkenes Using Activated Carbon-Based Cathodes.

Granular activated carbon (GAC) is used to sorb a broad range of halogenated contaminant classes, but spent GAC disposal is costly. Taking advantage of GAC's conductivity, this study evaluated the conversion of the GAC to cathodes for electrochemical reductive dehalogenation of 15 halogenated alkanes and alkenes exhibiting a diversity of structures (type of halogen, number of halogens, functional groups) and including contaminants of practical importance (e.g., trichloroethylene). Alkane degradation rates increased with the number of halogens and in the order: chlorine < bromine < iodine. Quantitative structure-activity relationships (QSARs) correlating experimental first-order degradation rate constants for alkanes with molecular descriptors associated with an outer-sphere one-electron transfer calculated using density functional theory indicated that correlations with molecular descriptors improved in the order: aqueous phase reduction potentials (E0,aq) < energy of the substrate's lowest unoccupied molecular orbital (ELUMO) < Marcus theory activation free energies (ΔG‡) ∼ gas-phase standard reduction free energies (ΔG0,gas). Chlorinated alkene degradation rates increased with decreasing number of chlorines, and QSAR correlations were opposite those of alkanes, indicating a different reaction mechanism. Degradation timescales ranged from 1 min to 3 h with halides as predominant products. These results suggest that the electrochemical reduction of halogenated alkanes and alkenes can be used to regenerate spent GAC.