Unveiling the dynamic active site of defective carbon-based electrocatalysts for hydrogen peroxide production.

Active sites identification in metal-free carbon materials is crucial for developing practical electrocatalysts, but resolving precise configuration of active site remains a challenge because of the elusive dynamic structural evolution process during reactions. Here, we reveal the dynamic active site identification process of oxygen modified defective graphene. First, the defect density and types of oxygen groups were precisely manipulated on graphene, combined with electrocatalytic performance evaluation, revealing a previously overlooked positive correlation relationship between the defect density and the 2 e- oxygen reduction performance. An electrocatalytic-driven oxygen groups redistribution phenomenon was observed, which narrows the scope of potential configurations of the active site. The dynamic evolution processes are monitored via multiple in-situ technologies and theoretical spectra simulations, resolving the configuration of major active sites (carbonyl on pentagon defect) and key intermediates (*OOH), in-depth understanding the catalytic mechanism and providing a research paradigm for metal-free carbon materials.

Second Sphere Effects Promote Formic Acid Dehydrogenation by a Single-Atom Gold Catalyst Supported on Amino-Substituted Graphdiyne.

Regulating the second sphere of homogeneous molecular catalysts is a common and effective method to boost their catalytic activities, while the second sphere effects have rarely been investigated for heterogeneous single-atom catalysts primarily due to the synthetic challenge for installing functional groups in their second spheres. Benefiting from the well-defined and readily tailorable structure of graphdiyne (GDY), an Au single-atom catalyst on amino-substituted GDY is constructed, where the amino group is located in the second sphere of the Au center. The Au atoms on amino-decorated GDY displayed superior activity for formic acid dehydrogenation compared with those on unfunctionalized GDY. The experimental studies, particularly the proton inventory studies, and theoretical calculations revealed that the amino groups adjacent to an Au atom could serve as proton relays and thus facilitate the protonation of an intermediate Au-H to generate H2 . Our study paves the way to precisely constructing the functional second sphere on single-atom catalysts.

Electronic Perturbation of Copper Single-Atom CO2 Reduction Catalysts in a Molecular Way.

Fine-tuning electronic structures of single-atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron-withdrawing/-donating groups, we show herein the electronic perturbation of Cu single-atom CO2 reduction catalysts in a molecular way. The elaborately introduced functional groups (-F, -H and -OMe) can regulate the valance state of Cuδ+ , which is found to be directly scaled with the selectivity of the electrochemical CO2 -to-CH4 conversion. An optimum CH4 Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F-substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cuδ+ centers adjusted by the electron-withdrawing group decrease the pKa of adsorbed H2 O, promoting the hydrogenation of intermediates toward the CH4 production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.

Defect-Engineered Cu-Based Nanomaterials for Efficient CO2 Reduction over Ultrawide Potential Window.

High conversion efficiency over a wide operating potential window is important for the practical application of CO2 reduction electrocatalysis, yet that remains a huge challenge in differentiating the competing CO2 reduction and H2 evolution. Here we introduce point defects (Sn doping) and planar defects (grain boundary) into the Cu substrate. This multidimensional defect integration strategy guides the fabrication of highly diluted SnCu polycrystal, which exhibits high Faradaic efficiencies (>95%) toward CO2 electroreduction over an ultrawide potential window (ΔE = 1.3 V). The theoretical study indicates that the introduction of Sn doping and grain boundary synergistically provides an optimized electronic effect, which helps suppress H2 evolution and promotes the hydrogenation of *CO2.

Single-Site Heterogeneous Organometallic Ir Catalysts Embedded on Graphdiyne: Structural Manipulation Beyond the Carbon Support.

Accurate control over the coordination circumstances of single-atom catalysts (SACs) is decisive to their intrinsic activity. Here, two single-site heterogeneous organometallic catalysts (SHOCs), Cp*Ir-L/GDY (L = OH- and Cl- ; Cp* = pentamethylcyclopentadienyl), with the fine-tuned local coordination and electronic structure of Ir sites, are constructed by anchoring Cp*Ir complexes on graphdiyne (GDY) matrix via a one-pot procedure. The spectroscopic studies and theoretical calculations indicate that the Ir atoms in Cp*Ir-Cl/GDY and Cp*Ir-OH/GDY have a much higher oxidation state than Ir in the SAC Ir/GDY. As a proof-of-principle demonstration, the GDY-supported SHOCs are used for formic acid dehydrogenation, which display a fivefold enhancement of catalytic activity compared with SAC Ir/GDY. The kinetic isotope effect and in situ Fourier-transform infrared studies reveal that the rate-limiting step is the ß-hydride elimination process, and Cp* on the Ir site accelerates the ß-hydride elimination reaction. The GDY-supported SHOCs integrate the merits of both SACs and molecular catalysts, wherein the isolated Ir anchored on GDY echoes with SACs' behavior, and the Cp* ligand enables precise structural and electronic regulation like molecular catalysts. The scheme of SHOCs adds a degree of freedom in accurate regulation of the local structure, the electronic property, and therefore the catalytic performance of single-atom catalysts.

Molecular Dynamics Beyond the Monolayer Adsorption as Derived from Langmuir Curve Fitting.

Langmuir adsorption model is a classic physical-chemical adsorption model and is widely used to describe the monolayer adsorption behavior at the material interface in environmental chemistry. Traditional adsorption dynamic modeling solely considered the surface physiochemical interaction between the adsorbent and adsorbate. The surface reaction dynamics resulting from the heterogeneous surface and intrinsic electronic structure of absorbents were rarely considered within the reported adsorption experiments. Herein, by employing the chlorine hybrid graphene oxide (GO-Cl) to adsorb Ag+ in an aqueous solution, complicated molecular dynamics significantly deviated from the monolayer adsorption mechanism, as suggested by Langmuir adsorption curve fitting, has been elucidated down to atomic scale. In the time-dependent Ag adsorption experiments, both Ag single atoms and Ag/AgCl nanoparticle heterostructures are observed to be formed sequentially on GO-Cl. These observations indicate that for the surface adsorption dynamics, not only the surface chemical adsorption process involved but also photoreduction and the C-Cl bond cleavage reaction has been heavily engaged within the GO-Cl interface, suggesting a much more complicated vision rather than the monolayered adsorption algorithm as derived from curve fitting. This study uses GO-Cl as a simple example to disclose the complicated adsorption dynamic process underneath Langmuir adsorption curve fitting. It advocates the necessity of imaging the interfacial atomic-scale dynamic structure with high-resolution microscopy techniques in modern adsorption studies, rather than simply explaining the adsorption dynamics relying on the curve fitting results due to the complicated physiochemical reactivity of the adsorbents.

Sacrificial W Facilitates Self-Reconstruction with Abundant Active Sites for Water Oxidation.

Water oxidation is an important reaction for multiple renewable energy conversion and storage-related devices and technologies. High-performance and stable electrocatalysts for the oxygen evolution reaction (OER) are urgently required. Bimetallic (oxy)hydroxides have been widely used in alkaline OER as electrocatalysts, but their activity is still not satisfactory due to insufficient active sites. In this research, A unique and efficient approach of sacrificial W to prepare CoFe (oxy)hydroxides with abundant active species for OER is presented. Multiple ex situ and operando/in situ characterizations have validated the self-reconstruction of the as-prepared CoFeW sulfides to CoFe (oxy)hydroxides in alkaline OER with synchronous W etching. Experiments and theoretical calculations show that the sacrificial W in this process induces metal cation vacancies, which facilitates the in situ transformation of the intermediate metal hydroxide to CoFe-OOH with more high-valence Co(III), thus creating abundant active species for OER. The Co(III)-rich environment endows the in situ formed CoFe oxyhydroxide with high catalytic activity for OER on a simple flat glassy carbon electrode, outperforming those not treated by the sacrificial W procedure. This research demonstrates the influence of etching W on the electrocatalytic performance, and provides a low-cost means to improve the active sites of the in situ self-reconstructed bimetallic oxyhydroxides for OER.

Bi2O3/BiO2 Nanoheterojunction for Highly Efficient Electrocatalytic CO2 Reduction to Formate.

Heterostructure engineering plays a vital role in regulating the material interface, thus boosting the electron transportation pathway in advanced catalysis. Herein, a novel Bi2O3/BiO2 heterojunction catalyst was synthesized via a molten alkali-assisted dealumination strategy and exhibited rich structural dynamics for an electrocatalytic CO2 reduction reaction (ECO2RR). By coupling in situ X-ray diffraction and Raman spectroscopy measurements, we found that the as-synthesized Bi2O3/BiO2 heterostructure can be transformed into a novel Bi/BiO2 Mott-Schottky heterostructure, leading to enhanced adsorption performance for CO2 and *OCHO intermediates. Consequently, high selectivity toward formate larger than 95% was rendered in a wide potential window along with an optimum partial current density of -111.42 mA cm-2 that benchmarked with the state-of-the-art Bi-based ECO2RR catalysts. This work reports the construction and fruitful structural dynamic insights of a novel heterojunction electrocatalyst for ECO2RR, which paves the way for the rational design of efficient heterojunction electrocatalysts for ECO2RR and beyond.

E_{8} Spectra of Quasi-One-Dimensional Antiferromagnet BaCo_{2}V_{2}O_{8} under Transverse Field.

We report ^{51}V NMR and inelastic neutron scattering (INS) measurements on a quasi-1D antiferromagnet BaCo_{2}V_{2}O_{8} under transverse field along the [010] direction. The scaling behavior of the spin-lattice relaxation rate above the Néel temperatures unveils a 1D quantum critical point (QCP) at H_{c}^{1D}≈4.7 T, which is masked by the 3D magnetic order. With the aid of accurate analytical analysis and numerical calculations, we show that the zone center INS spectrum at H_{c}^{1D} is precisely described by the pattern of the 1D quantum Ising model in a magnetic field, a class of universality described in terms of the exceptional E_{8} Lie algebra. These excitations are nondiffusive over a certain field range when the system is away from the 1D QCP. Our results provide an unambiguous experimental realization of the massive E_{8} phase in the compound, and open a new experimental route for exploring the dynamics of quantum integrable systems as well as physics beyond integrability.

Surface Functionalization of a γ-Graphyne-like Carbon Material via Click Chemistry.

Surface functionalization of carbon materials is of interest in many research fields, such as electrocatalysis, interfacial engineering, and supercapacitors. As an emerging carbon material, γ-graphyne has attracted broad attention. Herein, we report that the surface functionalization of a γ-graphyne-like carbon material (γ-G1) is achieved by immobilizing functional groups via the click chemistry. Texture analysis of aberration-corrected microscopy, X-ray photoelectron spectroscopy, and electrochemistry confirm the successful surface modification of γ-G1 through a strong covalent linkage 1,2,3-triazole. The direct linkage of functional groups on γ-G1 via the click chemistry represents a general method for preparing other functional materials by using γ-graphyne-like materials as a skeleton.

From Ru-bda to Ru-bds: a step forward to highly efficient molecular water oxidation electrocatalysts under acidic and neutral conditions.

Significant advances during the past decades in the design and studies of Ru complexes with polypyridine ligands have led to the great development of molecular water oxidation catalysts and understanding on the O-O bond formation mechanisms. Here we report a Ru-based molecular water oxidation catalyst [Ru(bds)(pic)2] (Ru-bds; bds2- = 2,2'-bipyridine-6,6'-disulfonate) containing a tetradentate, dianionic sulfonate ligand at the equatorial position and two 4-picoline ligands at the axial positions. This Ru-bds catalyst electrochemically catalyzes water oxidation with turnover frequencies (TOF) of 160 and 12,900 s-1 under acidic and neutral conditions respectively, showing much better performance than the state-of-art Ru-bda catalyst. Density functional theory calculations reveal that (i) under acidic conditions, the high valent Ru intermediate RuV=O featuring the 7-coordination configuration is involved in the O-O bond formation step; (ii) under neutral conditions, the seven-coordinate RuIV=O triggers the O-O bond formation; (iii) in both cases, the I2M (interaction of two M-O units) pathway is dominant over the WNA (water nucleophilic attack) pathway.

Size-Dependent Activity and Selectivity of Atomic-Level Copper Nanoclusters during CO/CO2 Electroreduction.

As a favorite descriptor, the size effect of Cu-based catalysts has been regularly utilized for activity and selectivity regulation toward CO2 /CO electroreduction reactions (CO2 /CORR). However, little progress has been made in regulating the size of Cu nanoclusters at the atomic level. Herein, the size-gradient Cu catalysts from single atoms (SAs) to subnanometric clusters (SCs, 0.5-1 nm) to nanoclusters (NCs, 1-1.5 nm) on graphdiyne matrix are readily prepared via an acetylenic-bond-directed site-trapping approach. Electrocatalytic measurements show a significant size effect in both the activity and selectivity toward CO2 /CORR. Increasing the size of Cu nanoclusters will improve catalytic activity and selectivity toward C2+ productions in CORR. A high C2+ conversion rate of 312 mA cm-2 with the Faradaic efficiency of 91.2 % are achieved at -1.0 V versus reversible hydrogen electrode (RHE) over Cu NCs. The activity/selectivity-size relations provide a clear understanding of mechanisms in the CO2 /CORR at the atomic level.

Regulating kinetics and thermodynamics of electrochemical nitrogen reduction with metal single-atom catalysts in a pressurized electrolyser.

Using renewable electricity to synthesize ammonia from nitrogen paves a sustainable route to making value-added chemicals but yet requires further advances in electrocatalyst development and device integration. By engineering both electrocatalyst and electrolyzer to simultaneously regulate chemical kinetics and thermodynamic driving forces of the electrocatalytic nitrogen reduction reaction (ENRR), we report herein stereoconfinement-induced densely populated metal single atoms (Rh, Ru, Co) on graphdiyne (GDY) matrix (formulated as M SA/GDY) and realized a boosted ENRR activity in a pressurized reaction system. Remarkably, under the pressurized environment, the hydrogen evolution reaction of M SA/GDY was effectively suppressed and the desired ENRR activity was strongly amplificated. As a result, the pressurized ENRR activity of Rh SA/GDY at 55 atm exhibited a record-high NH3 formation rate of 74.15 µg h-1⋅cm-2, a Faraday efficiency of 20.36%, and a NH3 partial current of 0.35 mA cm-2 at -0.20 V versus reversible hydrogen electrode, which, respectively, displayed 7.3-, 4.9-, and 9.2-fold enhancements compared with those obtained under ambient conditions. Furthermore, a time-independent ammonia yield rate using purified 15N2 confirmed the concrete ammonia electroproduction. Theoretical calculations reveal that the driving force for the formation of end-on N2* on Rh SA/GDY increased by 9.62 kJ/mol under the pressurized conditions, facilitating the ENRR process. We envisage that the cooperative regulations of catalysts and electrochemical devices open up the possibilities for industrially viable electrochemical ammonia production.

Novel Bi-Doped Amorphous SnOx Nanoshells for Efficient Electrochemical CO2 Reduction into Formate at Low Overpotentials.

Engineering novel Sn-based bimetallic materials could provide intriguing catalytic properties to boost the electrochemical CO2 reduction. Herein, the first synthesis of homogeneous Sn1- x Bix alloy nanoparticles (x up to 0.20) with native Bi-doped amorphous SnOx shells for efficient CO2 reduction is reported. The Bi-SnOx nanoshells boost the production of formate with high Faradaic efficiencies (>90%) over a wide potential window (-0.67 to -0.92 V vs RHE) with low overpotentials, outperforming current tin oxide catalysts. The state-of-the-art Bi-SnOx nanoshells derived from Sn0.80 Bi0.20 alloy nanoparticles exhibit a great partial current density of 74.6 mA cm-2 and high Faradaic efficiency of 95.8%. The detailed electrocatalytic analyses and corresponding density functional theory calculations simultaneously reveal that the incorporation of Bi atoms into Sn species facilitates formate production by suppressing the formation of H2 and CO.

Synergizing Mo Single Atoms and Mo2 C Nanoparticles on CNTs Synchronizes Selectivity and Activity of Electrocatalytic N2 Reduction to Ammonia.

Previous research of molybdenum-based electrocatalysts for nitrogen reduction reaction (NRR) has been largely considered on either isolated Mo single atoms (MoSAs) or Mo carbide particles (e.g., Mo2 C) separately, while an integrated synergy (MoSAs-Mo2 C) of the two has never been considered. The theoretical calculations show that the Mo single atoms and Mo2 C nanoparticles exhibit, respectively, different catalytic hydrogen evolution reaction and NRR selectivity. Therefore, a new role-playing synergistic mechanism can be well enabled for the multistep NRR, when the two are combined on the same N-doped carbon nanotubes (NCNTs). This hypothesis is confirmed experimentally, where the MoSAs-Mo2 C assembled on NCNTs (MoSAs-Mo2 C/NCNTs) yields an ammonia formation rate of 16.1 µg h-1 cmcat -2 at -0.25 V versus reversible hydrogen electrode, which is about four times that by the Mo2 C alone (Mo2 C/NCNTs) and 4.5 times that by the MoSAs alone (MoSAs/NCNTs). Moreover, the Faradic efficiency of the MoSAs-Mo2 C/NCNTs is raised up to twofold and sevenfold of the Mo2 C/NCNTs and MoSAs/NCNTs, respectively. The MoSAs-Mo2 C/NCNTs also demonstrate outstanding stability by the almost unchanged catalytic performance over 10 h of the chronoamperometric test. The present study provides a promising new prototype of synchronizing the selectivity and activity for the multistep catalytic reactions.

Microwave-assisted synthesis of porous and hollow α-Fe2O3/LaFeO3 nanostructures for acetone gas sensing as well as photocatalytic degradation of methylene blue.

To address the urgent issues of hazardous gas detection and the prevention of environmental pollution, various functional materials for gas sensing and catalytic reduction have been studied. Specifically, the p-type perovskite LaFeO3 has been studied widely because of its promising physicochemical properties. However, there remains several problems to develop a controllable synthesis of LaFeO3-based p-n heterojunctions. In this work, α-Fe2O3 was further compounded with LaFeO3 to form a porous and hollow α-Fe2O3/LaFeO3 heterojunction to improve its gas-sensing performance and photocatalytic efficiency via a microwave-assisted hydrothermal method. While evaluated as sensors of acetone gas, the optimized sample exhibits excellent performance, including a high response (48.3), excellent selectivity, good reversibility, fast response, and recovery ability. Furthermore, it is an efficient catalyst for the degradation of methylene blue. This can be attributed to the enhancement effect of its larger specific surface area, fast diffusion, enhanced surface activities, and p-n heterojunction. Additionally, this work provides a rapid and rational synthesis strategy to produce metal oxides with both enhanced gas-sensing performance and improved photocatalytic properties.

Universality of Heisenberg-Ising chain in external fields.

Motivated by the recent surge of transverse-field experiments on quasi-one-dimensional (1D) antiferromagnets Sr(Ba)Co2V2O8, we investigate the quantum phase transition (QPT) in a Heisenberg-Ising chain under a combination of two in-plane inter-perpendicular transverse fields and a four-period longitudinal field, where the in-plane transverse field is either uniform or staggered. We show that the model can be unitary mapped to the 1D transverse-field Ising model (1DTFIM) when the x and y  components of the spin interaction and the four-period field are absent. When these two terms are present, following both analytical and numerical efforts, we demonstrate that the system undergoes a second-order QPT with increasing transverse fields, where the critical exponents as well as the central charge fall into the universality of 1DTFIM. Our results naturally identify the 1DTFIM universality of 1D quantum phase transitions observed in the existed experiments in Sr(Ba)Co2V2O8 with transverse field applied along either [[Formula: see text]] or [[Formula: see text]] direction. Upon varying the tuning parameters, a critical surface with 1DTFIM universality is determined and silhouetted to exhibit the general presence of the universality in a much wider scope of models than conventional understanding. Our results provide a broad guiding framework to facilitate the experimental realization of 1DTFIM universality in real materials.

Quantum Critical Dynamics of a Heisenberg-Ising Chain in a Longitudinal Field: Many-Body Strings versus Fractional Excitations.

We report a high-resolution terahertz spectroscopic study of quantum spin dynamics in the antiferromagnetic Heisenberg-Ising spin-chain compound BaCo_{2}V_{2}O_{8} as a function of temperature and longitudinal magnetic field. Confined spinon excitations are observed in an antiferromagnetic phase below T_{N}≃5.5 K. In a field-induced gapless phase above B_{c}=3.8 T, we identify many-body string excitations as well as low-energy fractional psinon or antipsinon excitations by comparing to Bethe ansatz calculations. In the vicinity of B_{c}, the high-energy string excitations are found to have a dominant contribution to the spin dynamics as compared with the fractional excitations.

Exactly Solvable Points and Symmetry Protected Topological Phases of Quantum Spins on a Zig-Zag Lattice.

A large number of symmetry-protected topological (SPT) phases have been hypothesized for strongly interacting spin-1/2 systems in one dimension. Realizing these SPT phases, however, often demands fine-tunings hard to reach experimentally. And the lack of analytical solutions hinders the understanding of their many-body wave functions. Here we show that two kinds of SPT phases naturally arise for ultracold polar molecules confined in a zigzag optical lattice. This system, motivated by recent experiments, is described by a spin model whose exchange couplings can be tuned by an external field to reach parameter regions not studied before for spin chains or ladders. Within the enlarged parameter space, we find the ground state wave function can be obtained exactly along a line and at a special point, for these two phases, respectively. These exact solutions provide a clear physical picture for the SPT phases and their edge excitations. We further obtain the phase diagram by using infinite time-evolving block decimation and discuss the phase transitions between the two SPT phases and their experimental signatures.

Sono-advanced Fenton-like degradation of aromatic amines in textile dyeing sludge: efficiency and mechanisms.

In this paper, a novel strategy integrating ultrasound (US) with a Fenton-like (zero-valent iron/EDTA/air, ZEA) process was proposed for the removal of the refractory and carcinogenic aromatic amines (AAs) in textile dyeing sludge for the first time. The operating condition was optimized as 1.08 W/cm3 ultrasonic density, 15 g/L ZVI, and 1.0 mM EDTA, which could reach degradation efficiencies of 51.79% in US, 72.88% in ZEA, and 92.40% in US/ZEA system after 90-min reaction. Quenching experiments showed that electron transfer reactions generated by the iron ligands in ZEA brought about various reactive oxidative species (ROS), in which Fe (IV), O2˙-, and ˙OH dominated the degradation. US induced sludge disintegration by ultrasonic shear, proven by particle size decrease and supernatant organic matter upsurge, which helps ROS contact with those pollutants in the sludge cavities. Besides, US facilitated the iron redox cycle for oxygen activation by promoting the corrosion of ZVI and stripping considerable ferric ions from sludge iron oxides which were verified by SEM, XRF, and XPS. Graphical abstract.