Recycled Tandem Catalysts Promising Ultralow Overpotential Li-CO2 Batteries.

Lithium-carbon dioxide (Li-CO2 ) batteries are regarded as a prospective technology to relieve the pressure of greenhouse emissions but are confronted with sluggish CO2 redox kinetics and low energy efficiency. Developing highly efficient and low-cost catalysts to boost bidirectional activities is craved but remains a huge challenge. Herein, derived from the spent lithium-ion batteries, a tandem catalyst is subtly synthesized and significantly accelerates the CO2 reduction and evolution reactions (CO2 RR and CO2 ER) kinetics with an in-built electric field (BEF). Combining with the theoretical calculations and advanced characterization techniques, this work reveals that the designed interface-induced BEF regulates the adsorption/decomposition of the intermediates during CO2 RR and CO2 ER, endowing the recycled tandem catalyst with excellent bidirectional activities. As a result, the spent electronics-derived tandem catalyst exhibits remarkable bidirectional catalytic performance, such as an ultralow voltage gap of 0.26 V and an ultrahigh energy efficiency of 92.4%. Profoundly, this work affords new opportunities to fabricate low-cost electrocatalysts from recycled spent electronics and inspires fresh perceptions of interfacial regulation including but not limited to BEF to engineer better Li-CO2 batteries.

Essential role of lattice oxygen in methanol electrochemical refinery toward formate.

Developing technologies based on the concept of methanol electrochemical refinery (e-refinery) is promising for carbon-neutral chemical manufacturing. However, a lack of mechanism understanding and material properties that control the methanol e-refinery catalytic performances hinders the discovery of efficient catalysts. Here, using 18O isotope-labeled catalysts, we find that the oxygen atoms in formate generated during the methanol e-refinery reaction can originate from the catalysts' lattice oxygen and the O-2p-band center levels can serve as an effective descriptor to predict the catalytic performance of the catalysts, namely, the formate production rates and Faradaic efficiencies. Moreover, the identified descriptor is consolidated by additional catalysts and theoretical mechanisms from density functional theory. This work provides direct experimental evidence of lattice oxygen participation and offers an efficient design principle for the methanol e-refinery reaction to formate, which may open up new research directions in understanding and designing electrified conversions of small molecules.

Acidic enol electrooxidation-coupled hydrogen production with ampere-level current density.

Hydrogen production coupled with biomass upgrading is vital for future sustainable energy developments. However, most biomass electrooxidation reactions suffer from high working voltage and low current density, which substantially hinder large-scale industrial applications. Herein, we report an acidic hydrogen production system that combined anodic ascorbic acid electrooxidation with cathodic hydrogen evolution. Unlike C-H and O-H bonds cleavage with slow kinetics in conventional organic oxidation, the highly active enol structure in ascorbic acid allows for an ultralow overpotential of only 12 mV@10 mA/cm2 using Fe single-atom catalysts, and reaches 1 A/cm2 at only 0.75 V (versus reversible hydrogen electrode) with approximately 100% Faraday efficiency for hydrogen production. Furthermore, the fabricated two-electrode membrane-free electrolyser delivers an industrial current density of 2 A/cm2@1.1 V at 60 °C (2.63 kWh/Nm3 H2), which requires half of the electricity consumption in conventional water electrolysis (~5 kWh/Nm3 H2). This work provides a new avenue for achieving industrial-scale hydrogen production from biomass.

Multi-Domain versus Single-Domain: A Magnetic Field is Not a Must for Promoting Spin-Polarized Water Oxidation.

The reaction kinetics of spin-polarized oxygen evolution reaction (OER) can be enhanced by ferromagnetic (FM) catalysts under an external magnetic field. However, applying a magnetic field necessitates additional energy consumption and creates design difficulties for OER. Herein, we demonstrate that a single-domain FM catalyst without external magnetic fields exhibits a similar OER increment to its magnetized multi-domain one. The evidence is given by comparing the pH-dependent increment of OER on multi- and single-domain FM catalysts with or without a magnetic field. The intrinsic activity of a single-domain catalyst is higher than that of a multi-domain counterpart. The latter can be promoted to approach the former by the magnetization effect. Reducing the FM catalyst size into the single-domain region, the spin-polarized OER performance can be achieved without a magnetic field, illustrating an external magnetic field is not a requirement to reap the benefits of magnetic catalysts.

Navigating surface reconstruction of spinel oxides for electrochemical water oxidation.

Understanding and mastering the structural evolution of water oxidation electrocatalysts lays the foundation to finetune their catalytic activity. Herein, we demonstrate that surface reconstruction of spinel oxides originates from the metal-oxygen covalency polarity in the MT-O-MO backbone. A stronger MO-O covalency relative to MT-O covalency is found beneficial for a more thorough reconstruction towards oxyhydroxides. The structure-reconstruction relationship allows precise prediction of the reconstruction ability of spinel pre-catalysts, based on which the reconstruction degree towards the in situ generated oxyhydroxides can be controlled. The investigations of oxyhydroxides generated from spinel pre-catalysts with the same reconstruction ability provide guidelines to navigate the cation selection in spinel pre-catalysts design. This work reveals the fundamentals for manipulating the surface reconstruction of spinel pre-catalysts for water oxidation.

Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation.

Water electrolysis is a promising technique for carbon neutral hydrogen production. A great challenge remains at developing robust and low-cost anode catalysts. Many pre-catalysts are found to undergo surface reconstruction to give high intrinsic activity in the oxygen evolution reaction (OER). The reconstructed oxyhydroxides on the surface are active species and most of them outperform directly synthesized oxyhydroxides. The reason for the high intrinsic activity remains to be explored. Here, a study is reported to showcase the unique reconstruction behaviors of a pre-catalyst, thiospinel CoFe2 S4 , and its reconstruction chemistry for a high OER activity. The reconstruction of CoFe2 S4 gives a mixture with both Fe-S component and active oxyhydroxide (Co(Fe)Ox Hy ) because Co is more inclined to reconstruct as oxyhydroxide, while the Fe is more stable in Fe-S component in a major form of Fe3 S4 . The interface spin channel is demonstrated in the reconstructed CoFe2 S4 , which optimizes the energetics of OER steps on Co(Fe)Ox Hy species and facilitates the spin sensitive electron transfer to reduce the kinetic barrier of O-O coupling. The advantage is also demonstrated in a membrane electrode assembly (MEA) electrolyzer. This work introduces the feasibility of engineering the reconstruction chemistry of the precatalyst for high performance and durable MEA electrolyzers.

The effect of the hydroxyl group position on the electrochemical reactivity and product selectivity of butanediol electro-oxidation.

This article presents a study on the effect of the hydroxyl group position on the electro-oxidation of butanediols, including 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 1,4-butanediol. The effect of the hydroxyl group position in butanediols on their electro-oxidation reactivities is investigated by cyclic voltammetry, linear sweep voltammetry, chronopotentiometry and chronoamperometry in 1.0 M KOH. The results show that the closer the two hydroxyl groups are, the higher the reactivity, and the lower the anodic potential butanediol has. Moreover, the oxidation products from chronoamperometry are analyzed by means of HPLC and NMR. Some value-added products, such as 3-hydroxypropionic acid/3-hydroxypropionate, are produced. The DFT calculation indicates that the oxidation of vicinal diols responds to the conversion from a hydroxyl group to a carboxylate group, followed by C-C bond cleavage, where the carbon charge decreases. These results provide an insight into reactant selection for the electrochemical synthesis of value-added chemicals.

Enhanced oxygen evolution over dual corner-shared cobalt tetrahedra.

Developing efficient catalysts is of paramount importance to oxygen evolution, a sluggish anodic reaction that provides essential electrons and protons for various electrochemical processes, such as hydrogen generation. Here, we report that the oxygen evolution reaction (OER) can be efficiently catalyzed by cobalt tetrahedra, which are stabilized over the surface of a Swedenborgite-type YBCo4O7 material. We reveal that the surface of YBaCo4O7 possesses strong resilience towards structural amorphization during OER, which originates from its distinctive structural evolution toward electrochemical oxidation. The bulk of YBaCo4O7 composes of corner-sharing only CoO4 tetrahedra, which can flexibly alter their positions to accommodate the insertion of interstitial oxygen ions and mediate the stress during the electrochemical oxidation. The density functional theory calculations demonstrate that the OER is efficiently catalyzed by a binuclear active site of dual corner-shared cobalt tetrahedra, which have a coordination number switching between 3 and 4 during the reaction. We expect that the reported active structural motif of dual corner-shared cobalt tetrahedra in this study could enable further development of compounds for catalyzing the OER.

Lattice site-dependent metal leaching in perovskites toward a honeycomb-like water oxidation catalyst.

Metal leaching during water oxidation has been typically observed in conjunction with surface reconstruction on perovskite oxide catalysts, but the role of metal leaching at each geometric site has not been distinguished. Here, we manipulate the occurrence and process of surface reconstruction in two model ABO3 perovskites, i.e., SrSc0.5Ir0.5O3 and SrCo0.5Ir0.5O3, which allow us to evaluate the structure and activity evolution step by step. The occurrence and order of leaching of Sr (A-site) and Sc/Co (B-site) were controlled by tailoring the thermodynamic stability of B-site. Sr leaching from A-site mainly generates more electrochemical surface area for the reaction, and additional leaching of Sc/Co from B-site triggers the formation of a honeycomb-like IrOxHy phase with a notable increase in intrinsic activity. A thorough surface reconstruction with dual-site metal leaching induces an activity improvement by approximately two orders of magnitude, which makes the reconstructed SrCo0.5Ir0.5O3 among the best for water oxidation in acid.

Spin pinning effect to reconstructed oxyhydroxide layer on ferromagnetic oxides for enhanced water oxidation.

Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER, to manipulate the spin ordering of ferromagnetic OER catalysts (e.g., by magnetization) can reduce the kinetic barrier. However, most active OER catalysts are not ferromagnetic, which makes the spin manipulation challenging. In this work, we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxideFM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning, simple magnetization further increases the spin alignment and thus the OER activity, which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1st dehydrogenation to reduce the barrier for subsequent O-O coupling.

Spin-polarized oxygen evolution reaction under magnetic field.

The oxygen evolution reaction (OER) is the bottleneck that limits the energy efficiency of water-splitting. The process involves four electrons' transfer and the generation of triplet state O2 from singlet state species (OH- or H2O). Recently, explicit spin selection was described as a possible way to promote OER in alkaline conditions, but the specific spin-polarized kinetics remains unclear. Here, we report that by using ferromagnetic ordered catalysts as the spin polarizer for spin selection under a constant magnetic field, the OER can be enhanced. However, it does not applicable to non-ferromagnetic catalysts. We found that the spin polarization occurs at the first electron transfer step in OER, where coherent spin exchange happens between the ferromagnetic catalyst and the adsorbed oxygen species with fast kinetics, under the principle of spin angular momentum conservation. In the next three electron transfer steps, as the adsorbed O species adopt fixed spin direction, the OER electrons need to follow the Hund rule and Pauling exclusion principle, thus to carry out spin polarization spontaneously and finally lead to the generation of triplet state O2. Here, we showcase spin-polarized kinetics of oxygen evolution reaction, which gives references in the understanding and design of spin-dependent catalysts.

Engineering High-Spin State Cobalt Cations in Spinel Zinc Cobalt Oxide for Spin Channel Propagation and Active Site Enhancement in Water Oxidation.

Spinel zinc cobalt oxide (ZnCo2 O4 ) is not considered as a superior catalyst for the electrochemical oxygen evolution reaction (OER), which is the bottleneck reaction in water-electrolysis. Herein, taking advantage of density functional theory (DFT) calculations, we find that the existence of low-spin (LS) state cobalt cations hinders the OER activity of spinel zinc cobalt oxide, as the t2g 6 eg 0 configuration gives rise to purely localized electronic structure and exhibits poor binding affinity to the key reaction intermediate. Increasing the spin state of cobalt cations in spinel ZnCo2 O4 is found to propagate a spin channel to promote spin-selected charge transport during OER and generate better active sites for intermediates adsorption. The experiments find increasing the calcination temperature a facile approach to engineer high-spin (HS) state cobalt cations in ZnCo2 O4 , while not working for Co3 O4 . The activity of the best spin-state-engineered ZnCo2 O4 outperforms other typical Co-based oxides.

Anodic Oxidation Enabled Cation Leaching for Promoting Surface Reconstruction in Water Oxidation.

A rational design for oxygen evolution reaction (OER) catalysts is pivotal to the overall efficiency of water electrolysis. Much work has been devoted to understanding cation leaching and surface reconstruction of very active electrocatalysts, but little on intentionally promoting the surface in a controlled fashion. We now report controllable anodic leaching of Cr in CoCr2 O4 by activating the pristine material at high potential, which enables the transformation of inactive spinel CoCr2 O4 into a highly active catalyst. The depletion of Cr and consumption of lattice oxygen facilitate surface defects and oxygen vacancies, exposing Co species to reconstruct into active Co oxyhydroxides differ from CoOOH. A novel mechanism with the evolution of tetrahedrally coordinated surface cation into octahedral configuration via non-concerted proton-electron transfer is proposed. This work shows the importance of controlled anodic potential in modifying the surface chemistry of electrocatalysts.

Spin-Related Electron Transfer and Orbital Interactions in Oxygen Electrocatalysis.

Oxygen evolution and reduction reactions play a critical role in determining the efficiency of the water cycling (H2 O ⇔ H2 + 1 2 O2 ), in which the hydrogen serves as the energy carrier. That calls for a comprehensive understanding of oxygen electrocatalysis for efficient catalyst design. Current opinions on oxygen electrocatalysis have been focused on the thermodynamics of the reactant/intermediate adsorption on the catalysts. Because the oxygen molecule is paramagnetic, its production from or its reduction to diamagnetic hydroxide/water involves spin-related electron transfer. Both electron transfer and orbital interactions between the catalyst and the reactant/intermediate show spin-dependent character, making the reaction kinetics and thermodynamics sensitive to the spin configurations. Herein, a brief introduction on the spintronic explanation of the catalytic phenomena on oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is given. The local spin configurations and orbital interactions in the benchmark transition-metal-based catalysts for OER and ORR are analyzed as examples. To further understand the spintronic oxygen electrocatalysis and to develop more efficient spintronic catalysts, the challenges are summarized and future opportunities proposed. Spin electrocatalysis may emerge as an important topic in the near future and help integrate a comprehensive understanding of oxygen electrocatalysis.

Impact Factors of Empathy in Mainland Chinese Youth.

Empathy was investigated in 592 Mainland Chinese youth using the Interpersonal Reactivity Index. Participants' empathy-related information covering demographic traits, emotional wellness, as well as academic and social problems were recorded. Results of Classification and Regression Tree (CART) analysis showed that emotional empathy, cognitive empathy, and empathy-related personal distress was impacted by inherited traits (e.g., sex), acquired traits (e.g., study major), and a combination of both aspects, respectively. Moreover, empathy was found to be higher in youth in a vulnerable social position (i.e., outlander, female, and ethnic minority) than those in a dominant one (i.e., local, male, and ethnic majority). It was also found that personal distress, rather than empathy, was significantly correlated with academic, social, and emotional problems in the youth cohort. Hence, the current study provided an innovative observation of the relationships between empathy, personal distress, ethnicity, social vulnerability, wellness, study major, and other key characteristics in Mainland Chinese youth.

Constructing an Adaptive Heterojunction as a Highly Active Catalyst for the Oxygen Evolution Reaction.

Electrochemical water splitting is of prime importance to green energy technology. Particularly, the reaction at the anode side, namely the oxygen evolution reaction (OER), requires a high overpotential associated with OO bond formation, which dominates the energy-efficiency of the whole process. Activating the anionic redox chemistry of oxygen in metal oxides, which involves the formation of superoxo/peroxo-like (O2 )n - , commonly occurs in most highly active catalysts during the OER process. In this study, a highly active catalyst is designed: electrochemically delithiated LiNiO2 , which facilitates the formation of superoxo/peroxo-like (O2 )n - species, i.e., NiOO*, for enhancing OER activity. The OER-induced surface reconstruction builds an adaptive heterojunction, where NiOOH grows on delithiated LiNiO2 (delithiated-LiNiO2 /NiOOH). At this junction, the lithium vacancies within the delithiated LiNiO2 optimize the electronic structure of the surface NiOOH to form stable NiOO* species, which enables better OER activity. This finding provides new insight for designing highly active catalysts with stable superoxo-like/peroxo-like (O2 )n - for water oxidation.

Surface Composition Dependent Ligand Effect in Tuning the Activity of Nickel-Copper Bimetallic Electrocatalysts toward Hydrogen Evolution in Alkaline.

Exploring efficient and low-cost electrocatalysts for hydrogen evolution reaction (HER) in alkaline media is critical for developing anion exchange membrane electrolyzers. The key to a rational catalyst design is understanding the descriptors that govern the alkaline HER activity. Unfortunately, the principles that govern the alkaline HER performance remain unclear and are still under debate. By studying the alkaline HER at a series of NiCu bimetallic surfaces, where the electronic structure is modulated by the ligand effect, we demonstrate that alkaline HER activity can be correlated with either the calculated or the experimental-measured d band center (an indicator of hydrogen binding energy) via a volcano-type relationship. Such correlation indicates the descriptor role of the d band center, and this hypothesis is further supported by the evidence that combining Ni and Cu produces a variety of adsorption sites, which possess near-optimal hydrogen binding energy. Our finding broadens the applicability of d band theory to activity prediction of metal electrocatalysts and may offer an insightful understanding of alkaline HER mechanism.

Electrochemical Oxidation of Nitrogen towards Direct Nitrate Production on Spinel Oxides.

Nitrates are widely used as fertilizer and oxidizing agents. Commercial nitrate production from nitrogen involves high-temperature-high-pressure multi-step processes. Therefore, an alternative nitrate production method under ambient environment is of importance. Herein, an electrochemical nitrogen oxidation reaction (NOR) approach is developed to produce nitrate catalyzed by ZnFex Co2-x O4 spinel oxides. Theoretical and experimental results show Fe aids the formation of the first N-O bond on the *N site, while high oxidation state Co assists in stabilizing the absorbed OH- for the generation of the second and third N-O bonds. Owing to the concerted catalysis, the ZnFe0.4 Co1.6 O4 oxide demonstrates the highest nitrate production rate of 130±12 µmol h-1 gMO -1 at an applied potential of 1.6 V versus the reversible hydrogen electrode (RHE).

Antiferromagnetic Inverse Spinel Oxide LiCoVO4 with Spin-Polarized Channels for Water Oxidation.

Exploring highly efficient catalysts for the oxygen evolution reaction (OER) is essential for water electrolysis. Cost-effective transition-metal oxides with reasonable activity are raising attention. Recently, OER reactants' and products' differing spin configurations have been thought to cause slow reaction kinetics. Catalysts with magnetically polarized channels could selectively remove electrons with opposite magnetic moment and conserve overall spin during OER, enhancing triplet state oxygen molecule evolution. Herein, antiferromagnetic inverse spinel oxide LiCoVO4 is found to contain d7 Co2+ ions that can be stabilized under active octahedral sites, possessing high spin states S = 3/2 (t2g 5 eg 2 ). With high spin configuration, each Co2+ ion has an ideal magnetic moment of 3 µB , allowing the edge-shared Co2+ octahedra in spinel to be magnetically polarized. Density functional theory simulation results show that the layered antiferromagnetic LiCoVO4 studied contains magnetically polarized channels. The average magnetic moment (µave ) per transition-metal atom in the spin conduction channel is around 2.66 µB . Such channels are able to enhance the selective removal of spin-oriented electrons from the reactants during the OER, which facilitates the accumulation of appropriate magnetic moments for triplet oxygen molecule evolution. In addition, the LiCoVO4 reported has been identified as an oxide catalyst with excellent OER activity.

Significance of Engineering the Octahedral Units to Promote the Oxygen Evolution Reaction of Spinel Oxides.

The clean energy carrier, hydrogen, if efficiently produced by water electrolysis using renewable energy input, would revolutionize the energy landscape. It is the sluggish oxygen evolution reaction (OER) at the anode of water electrolyzer that limits the overall efficiency. The large spinel oxide family is widely studied due to their low cost and promising OER activity. As the distribution of transition metal (TM) cations in octahedral and tetrahedral site is an important variable controlling the electronic structure of spinel oxides, the TM geometric effect on OER is discussed. The dominant role of octahedral sites is found experimentally and explained by computational studies. The redox-active TM locating at octahedral site guarantees an effective interaction with the oxygen at OER conditions. In addition, the adjacent octahedral centers in spinel act cooperatively in promoting the fast OER kinetics. In remarkable contrast, the isolated tetrahedral TM centers in spinel prohibit the OER mediated by dual-metal sites. Furthermore, various spinel oxides preferentially expose octahedral-occupied cations on the surface, making the octahedral cations easily accessible to the reactants. The future perspectives and challenges in advancing fundamental understanding and developing robust spinel catalysts are discussed.