Design, Synthesis, and 3D-QASR of 2-Ar-1,2,3-triazole Derivatives Containing Hydrazide as Potential Fungicides.

A series of novel 2-Ar-1,2,3-triazole derivatives were designed and synthesized based on our previously discovered active compound 6d against Rhizoctonia solani. Most of these compounds exhibited good antifungal activity against R. solani at a concentration of 25 µg/mL. Based on the results of biological activity, we established a three-dimensional quantitative structure-activity relationship (3D-QSAR) model that guided the synthesis of compound 7y. Compound 7y exhibited superior activity against R. solani (EC50 = 0.47 µg/mL) compared to the positive controls hymexazol (EC50 = 12.80 µg/mL) and tebuconazole (EC50 = 0.87 µg/mL). Furthermore, compound 7y demonstrated better protective activity than the aforementioned two commercial fungicides in both detached leaf assays and greenhouse experiments, achieving 56.21% and 65.75% protective efficacy, respectively, at a concentration of 100 µg/mL. The ergosterol content was determined and molecular docking was performed to explore the mechanism of these active molecules. DFT calculation and MEP analysis were performed to illustrate the results of this study. These results suggest that compound 7y could serve as a novel 2-Ar-1,2,3-triazole lead compound for controlling R. solani.

Theoretical Study of Single-Atom Catalysts for Hydrogen Evolution Reaction Based on BiTeBr Monolayer.

Developing an inexpensive and efficient catalyst for a hydrogen evolution reaction (HER) is an effective measure to alleviate the energy crisis. Single-atom catalysts (SACs) based on Janus materials demonstrated promising prospects for the HER. Herein, density functional theory calculations were conducted to systematically investigate the performance of SACs based on the BiTeBr monolayer. Among the one hundred and forty models that were constructed, fourteen SACs with potential HER activity were selected. Significantly, the SAC, in which a single Ru atom is anchored on a BiTeBr monolayer with a Bi vacancy (RuS2/VBi-BiTeBr), exhibits excellent HER activity with an ultra-low |ΔGH*| value. A further investigation revealed that RuS2/VBi-BiTeBr tends to react through the Volmer-Heyrovsky mechanism. An electronic structure analysis provided deeper insights into this phenomenon. This is because the Tafel pathway requires overcoming steric hindrance and disrupting stable electron filling states, making it challenging to proceed. This study finally employed constant potential calculations, which approximate experimental situations. The results indicated that the ΔGH* value at pH = 0 is 0.056 eV for RuS2/VBi-BiTeBr, validating the rationality of the traditional Computational Hydrogen Electrode (CHE) method for performance evaluation in this system. This work provides a reference for the research of new HER catalysts.

Cu-phen Coordination Enabled Selective Electrocatalytic Reduction of CO2 to Methane.

Manipulation of selectivity in the catalytic electrochemical carbon dioxide reduction reaction (eCO2RR) poses significant challenges due to inevitable structure reconstruction. One approach is to develop effective strategies for controlling reaction pathways to gain a deeper understanding of mechanisms in robust CO2RR systems. In this work, by precise introduction of 1,10-phenanthroline as a bidentate ligand modulator, the electronic property of the copper site was effectively regulated, thereby directing selectivity switch. By modification of [Cu3(btec)(OH)2]n, the use of [Cu2(btec)(phen)2]n·(H2O)n achieved the selectivity switch from ethylene (faradaic efficiency (FE) = 41%, FEC2+ = 67%) to methane (FECH4 = 69%). Various in situ spectroscopic characterizations revealed that [Cu2(btec)(phen)2]n·(H2O)n promoted the hydrogenation of *CO intermediates, leading to methane generation instead of dimerization to form C2+ products. Acting as a delocalized π-conjugation scaffold, 1,10-phenanthroline in [Cu2(btec)(phen)2]n·(H2O)n helps stabilize Cuδ+. This work presents a novel approach to regulate the coordination environment of active sites with the aim of selectively modulating the CO2RR.

Highly efficient anion exchange membrane water electrolyzers via chromium-doped amorphous electrocatalysts.

In-depth comprehension and modulation of the electronic structure of the active metal sites is crucial to enhance their intrinsic activity of electrocatalytic oxygen evolution reaction (OER) toward anion exchange membrane water electrolyzers (AEMWEs). Here, we elaborate a series of amorphous metal oxide catalysts (FeCrOx, CoCrOx and NiCrOx) with high performance AEMWEs by high-valent chromium dopant. We discover that the positive effect of the transition from low to high valence of the Co site on the adsorption energy of the intermediate and the lower oxidation barrier is the key factor for its increased activity by synchrotron radiation in-situ techniques. Particularly, the CoCrOx anode catalyst achieves the high current density of 1.5 A cm-2 at 2.1 V and maintains for over 120 h with attenuation less than 4.9 mV h-1 in AEMWE testing. Such exceptional performance demonstrates a promising prospect for industrial application and providing general guidelines for the design of high-efficiency AEMWEs systems.

First-Principles Insights into Tungsten Semicarbide-Based Single-Atom Catalysts: Single-Atom Migration and Mechanisms in Oxygen Reduction.

Understanding the structural evolution of single-atom catalysts (SACs) in catalytic reactions is crucial for unraveling their catalytic mechanisms. In this study, we utilize density functional theory calculations to delve into the active phase evolution and the oxygen reduction reaction (ORR) mechanism of tungsten semicarbide-based transition metal SACs (TM1/W2C). The stable crystal phases and optimal surface exposures of W2C are identified by using ab initio atomistic thermodynamics simulations. Focusing on the W-terminated (001) surface, we screen 13 stable TM1/W2C variants, ultimately selecting Pt1/W2C(001) as our primary model. The surface Pourbaix diagram, mapped for this model under ORR conditions, reveals dynamic Pt1 migration on the surface, triggered by surface oxidation. This discovery suggests a novel single-atom evolution pathway. Remarkably, this single-atom migration behavior is also discerned in seven other group VIII SACs, enhancing both their catalytic activity and their stability. Our findings offer insights into the evolution of active phases in SACs, considering substrate structural arrangement, single-atom incorporation, and self-optimization of catalysts under various conditions.

Self-Assembly Intermetallic PtCu3 Core with High-Index Faceted Pt Shell for High-Efficiency Oxygen Reduction.

Rational design of well-defined active sites is crucial for promoting sluggish oxygen reduction reactions. Herein, leveraging the surfactant-oriented and solvent-ligand effects, we develop a facile self-assembly strategy to construct a core-shell catalyst comprising a high-index Pt shell encapsulating a PtCu3 intermetallic core with efficient oxygen-reduction performance. Without undergoing a high-temperature route, the ordered PtCu3 is directly fabricated through the accelerated reduction of Cu2+, followed by the deposition of the remaining Pt precursor onto its surface, forming high-index steps oriented by the steric hindrance of surfactant. This approach results in a high half-wave potential of 0.911 V versus reversible hydrogen electrode, with negligible deactivation even after 15000-cycle operation. Operando spectroscopies identify that this core-shell catalyst facilitates the conversion of oxygen-involving intermediates and ensures antidissolution ability. Theoretical investigations rationalize that this improvement is attributed to reinforced electronic interactions around high-index Pt, stabilizing the binding strength of rate-determining OHads species.

Boosting Electrocatalytic Ammonia Synthesis via Synergistic Effect of Iron-Based Single Atoms and Clusters.

Electrocatalytic reduction of nitrate to ammonia (NO3RR) is gaining attention for low carbon emissions and environmental protection. However, low ammonia production rate and poor selectivity have remained major challenges in this multi-proton coupling process. Herein, we report a facile strategy toward a novel Fe-based hybrid structure composed of Fe single atoms and Fe3C atomic clusters that demonstrates outstanding performance for synergistic electrocatalytic NO3RR. By operando synchrotron Fourier transform infrared spectroscopy and theoretical computation, we clarify that Fe single atoms serve as the active site for NO3RR, while Fe3C clusters facilitate H2O dissociation to provide protons (*H) for continued hydrogenation reactions. As a result, the Fe-based electrocatalyst exhibits ammonia Faradaic efficiency of nearly 100%, with a corresponding production rate of 24768 µg h-1 cm-2 at -0.4 V vs RHE, exceeding most reported metal-based catalysts. This research provides valuable guidance toward multi-step reactions.

Highly dispersed ultrafine PtCo alloy nanoparticles on unique composite carbon supports for proton exchange membrane fuel cells.

The design of highly efficient and robust platinum-based electrocatalysts is pivotal for proton exchange membrane fuel cells (PEMFC). One of the long-standing issues for PEMFC is the rapid deactivation of the catalyst under working conditions. Here, we report a simple synthesis strategy for ultrafine PtCo alloy nanoparticles loaded on a unique carbon support derived from a zeolitic imidazolate framework-67 (ZIF-67) and Ketjen Black (KB) composite, exhibiting a remarkable catalytic performance toward the oxygen reduction reaction (ORR) and PEMFC. Benefitting from the N-doping and wide pore size distribution of the composite carbon supports, the growth of PtCo nanoparticles can be evenly restricted, leading to a uniform distribution. The Pt-integrated catalyst delivers an outstanding electrochemical performance with a mass activity that is 8.6 times higher than that of the commercial Pt/C catalyst. Impressively, the accelerated durability test (ADT) demonstrates that the hybrid carbon support can significantly enhance the durability. Theoretical simulations highlight the synergistic contribution between the supports and the PtCo nanoparticles. Moreover, hydrogen-oxygen fuel cells assembled with the catalyst exhibited a high power density of 1.83 W cm-2 at 4 A cm-2. These results provide a new opportunity to design advanced catalysts for PEMFC.

A First-Principles Study of Regulating Spin States of MoSi2N4 Supported Single-Atom Catalysts Via Doping Strategy for Enhancing Electrochemical Nitrogen Fixation Activity.

Regulating the spin states of catalysts to enhance activity is fascinating but challenging. Herein, by using first-principles calculations, single transition-metal (TM) atoms Mo, Re, and Os embedded in nitrogen vacancy of the MoSi2N4 monolayer (TM1/VN-MoSi2N4) were screened out as potential catalysts for electrochemical nitrogen reduction reaction to ammonia. Our findings suggest that the spin states of these active centers can be precisely and gradually tuned through a simple doping strategy. Additionally, doping one O atom into the Mo1/VN-MoSi2N4 system as an example significantly improves catalytic activity. The spin state of Mo1 transitions from high to intermediate while simultaneously breaking the C3v symmetry of the supported atom. These factors synergistically lead to better orbital overlap between the catalyst and intermediates, facilitating subsequent protonation processes and overall catalytic activity. This work provides novel insight into designing, precisely controlling, and revisiting the spin-related catalytic performance in heterogeneous catalysis.

Proposal of spin crossover as a reversible switch of catalytic activity for the oxygen evolution reaction in two dimensional metal-organic frameworks.

The development of oxygen evolution reaction (OER) catalysts with high activity and controllability is crucial for clean energy conversion and storage but remains a challenge. Here, based on first-principles calculations, we propose to utilize spin crossover (SCO) in two-dimensional (2D) metal-organic frameworks (MOFs) to achieve reversible control of OER catalytic activity. The theoretical design of a 2D square lattice MOF with Co as nodes and tetrakis-substituted cyanimino squaric acid (TCSA) as ligands, which transforms between the high spin (HS) and the low spin (LS) state by applying an external strain (∼2%), confirms our proposal. In particular, the HS-LS spin state transition of Co(TCSA) considerably regulates the adsorption strength of the key intermediate HO* in the OER process, resulting in a significant reduction of the overpotential from 0.62 V in the HS state to 0.32 V in the LS state, thus realizing a reversible switch for the activity of the OER. Moreover, the high activity of the LS state is confirmed by microkinetic and constant potential method simulations.

Promoting Oxygen Reduction Reaction on Carbon-based Materials by Selective Hydrogen Bonding.

Electrochemical oxygen reduction reaction (ORR) is fundamental for many energy conversion and storage devices. Selective tuning of *OOH/*OH adsorption energy to break the intrinsic scaling limitation (ΔG*OOH =ΔG*OH +3.2 eV) is effective in optimizing the ORR limiting potential (UL ), which is practically challenging to achieve by constructing a particular catalyst. Herein, using first-principles calculations, we elucidated how to rationally plant an additional *OH that can selectively interact with the ORR intermediate of *OOH via hydrogen bonding, while not affecting the *OH intermediate. Guided by the design principle, we successfully tailored a series of novel carbon-based catalysts, with merits of low-cost, long-lasting, synthesis feasibility, exhibiting a high UL (1.06 V). Our proposed strategy comes up with a new linear scaling relationship of ΔG*OOH =ΔG*OH +2.84 eV. This approach offers a great possibility for the rational design of efficient catalysts for ORR and other chemical reactions.

Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts.

The transformation from metal nanocluster catalysts to metal single-atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single-atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C. Using ex-situ microscopy and spectroscopy, we comprehensively monitored the structural evolution of Pd species though the whole atomization process. Theoretical calculation revealed that the structural instability caused by remaining Cl ligands was the main reason for this low-temperature transformation. The present atomization strategy and mechanistic knowledge for the conversion from cluster to atomic dispersion provides guidelines for the rational design of ADCs.

Understanding Synergistic Catalysis on Cu-Se Dual Atom Sites via Operando X-ray Absorption Spectroscopy in Oxygen Reduction Reaction.

The construction and understanding of synergy in well-defined dual-atom active sites is an available avenue to promote multistep tandem catalytic reactions. Herein, we construct a dual-hetero-atom catalyst that comprises adjacent Cu-N4 and Se-C3 active sites for efficient oxygen reduction reaction (ORR) activity. Operando X-ray absorption spectroscopy coupled with theoretical calculations provide in-depth insights into this dual-atom synergy mechanism for ORR under realistic device operation conditions. The heteroatom Se modulator can efficiently polarize the charge distribution around symmetrical Cu-N4 moieties, and serve as synergistic site to facilitate the second oxygen reduction step simultaneously, in which the key OOH*-(Cu1 -N4 ) transforms to O*-(Se1 -C2 ) intermediate on the dual-atom sites. Therefore, this designed catalyst achieves satisfied alkaline ORR activity with a half-wave potential of 0.905 V vs. RHE and a maximum power density of 206.5 mW cm-2 in Zn-air battery.

Open Nitrogen Site-Induced Kinetic Resolution and Catalysis of a Gold Nanocluster.

The emerging metal nanocluster provides a platform for the investigation of structural features, unique properties, and structure-property correlation of nanomaterials at the atomic level. Construction of open sites on the surface of the metal nanocluster is a long-pursued but challenging goal. Herein, we realized the construction of "open organic sites" in a metal nanocluster for the first time. Specifically, we introduce the PNP (2,6-bis(diphenylphosphinomethyl)pyridine) pincer ligand in the synthesis of the gold nanocluster, enabling the construction of a structurally precise Au8(PNP)4 nanocluster. The rigidity and the unique bonding mode of PNP lead to open nitrogen sites on the surface of the Au8(PNP)4 nanocluster, which have been utilized as multifunctional sites in this work for efficient kinetic resolution and catalysis. The gold pincer nanocluster and the open nitrogen site-induced performance will be enlightening for the construction of multifunctional metal nanoclusters.

Enhanced Electron-Hole Separation in Phosphorus-Coordinated Co Atom on g-C3N4 toward Photocatalytic Overall Water Splitting.

Revealing the decoration mode of g-C3N4 and understanding the physical mechanism of overall water splitting is important for the further improvement of the photocatalytic activity of g-C3N4-based materials. With core level shift and molecular dynamics simulations based on first-principles calculations, Co1(PHx)3 anchored on the triazine of g-C3N4 is determined as a stable single-atom catalyst with high efficiency for photocatalytic overall water splitting. The separated spin-polarized charge density distribution of valence-band maximum and conduction-band minimum states is beneficial for the long lifetime of photoexcited electrons and holes. An anchored Co single atom site is the active site for oxygen evolution reaction, and nitrogen atoms act as active sites for hydrogen evolution reaction. This new decoration mode of g-C3N4 opens a possible way to functionalize g-C3N4 on both triazine and void sites to realize the separation of OER and hydrogenation reaction by water splitting.

Actinide-uranium single-atom catalysis for electrochemical nitrogen fixation.

Actinide-based catalysts have been regarded as promising candidates for N2 fixation owing to their unique 5f orbital with flexible oxidation states. Herein, we report for the first time the dispersion of uranium (U) single atoms on TiO2 nanosheets via oxygen vacancy confinement for N2 electroreduction. The single-atom U catalyst exhibited a high NH3 yield of 40.57 µg h-1 mg-1, with a reasonably high Faraday efficiency of 25.77%, ranking first among the reported nitrogen-free catalysts. Isotope-labeling operando synchrotron infrared spectroscopy verifies that the key *N2Hy intermediate species was derived from the N2 gas of the feed. By using operando X-ray absorption spectroscopy, we found enhanced metal-support interaction between U single atoms and TiO2 lattice with more U-Olatt coordination under working conditions. Theoretical simulations suggest that the evolved 1Oads-U-4Olatt moieties act as a critical electron-feedback center, lowering the thermodynamic energy barrier for the N2 dissociation and the first hydrogenation step. This work provides the possibility of tailoring the interaction between metal active sites and supports for designing high-performance actinide-based single-atom catalysts.

Mechanistic insights into CO2 conversion chemistry of copper bis-(terpyridine) molecular electrocatalyst using accessible operando spectrochemistry.

The implementation of low-cost transition-metal complexes in CO2 reduction reaction (CO2RR) is hampered by poor mechanistic understanding. Herein, a carbon-supported copper bis-(terpyridine) complex enabling facile kilogram-scale production of the catalyst is developed. We directly observe an intriguing baton-relay-like mechanism of active sites transfer by employing a widely accessible operando Raman/Fourier-transform infrared spectroscopy analysis coupled with density functional theory computations. Our analyses reveal that the first protonation step involves Cu-N bond breakage before the *COOH intermediate forms exclusively at the central N site, followed by an N-to-Cu active site transfer. This unique active site transfer features energetically favorable *CO formation on Cu sites, low-barrier CO desorption and reversible catalyst regeneration, endowing the catalyst with a CO selectively of 99.5 %, 80 h stability, and a turn-over efficiency of 9.4 s-1 at -0.6 V vs. the reversible hydrogen electrode in an H-type cell configuration. We expect that the approach and findings presented here may accelerate future mechanistic studies of next-generation CO2RR electrocatalysts.

Structural and electrocatalytic properties of copper clusters: A study via deep learning and first principles.

Determining the atomic structure of clusters has been a long-term challenge in theoretical calculations due to the high computational cost of density-functional theory (DFT). Deep learning potential (DP), as an alternative way, has been demonstrated to be able to conduct cluster simulations with close-to DFT accuracy but at a much lower computational cost. In this work, we update 34 structures of the 41 Cu clusters with atomic numbers ranging from 10 to 50 by combining global optimization and the DP model. The calculations show that the configuration of small Cun clusters (n = 10-15) tends to be oblate and it gradually transforms into a cage-like configuration as the size increases (n > 15). Based on the updated structures, their relative stability and electronic properties are extensively studied. In addition, we select three different clusters (Cu13, Cu38, and Cu49) to study their electrocatalytic ability of CO2 reduction. The simulation indicates that the main product is CO for these three clusters, while the selectivity of hydrocarbons is inhibited. This work is expected to clarify the ground-state structures and fundamental properties of Cun clusters, and to guide experiments for the design of Cu-based catalysts.

Utilizing High Coordination Diversity in Carbon Nanocone Supported Catalytic Single-Atom Sites for Screening of Optimal Activity.

The hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) are crucial in various energy conversion and storage technologies. Performances of catalysts are appreciably affected by the adsorption energies of key reaction intermediates, whereas the active site engineering to achieve optimal adsorption energy remains challenging. Herein, using density functional theory calculations, we proposed a novel design of transition metal single-atom active sites supported by carbon nanocone (CNC) with high coordination diversity. The particularly diversified electronic states of CNC carbon atoms endow varying coordination to the metal active sites, which then results in a near-continuum distribution of adsorption energies for key intermediates. With this mode, 33 CNC-based active sites exhibit outstanding catalytic potential for the HER with near-zero free energy barriers. Meanwhile, five distinct Cu-N3 active sites can serve as promising candidates for the ORR with low overpotentials. Our work suggests a new strategy of making nanocone-based single-atom catalysts with promising catalytic performance.

Improving the Activity of Electrocatalysts toward the Hydrogen Evolution Reaction, the Oxygen Evolution Reaction, and the Oxygen Reduction Reaction via Modification of Metal and Ligand of Conductive Two-Dimensional Metal-Organic Frameworks.

Exploring efficient and stable electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution and reduction reactions (OER and ORR) is vital to the development of renewable energy technologies. Herein, on the basis of density functional theory (DFT) calculations, we systematically investigated 30 TMNxO4-x-HTP (TM = Fe, Co, Ni, Ru, Rh and Pd; x = 0-4; HTP refers to hexatriphenylene) analogs of conductive two-dimensional (2D) metal-organic frameworks (MOFs) as potential catalysts for HER, OER, and ORR. The results show the good stabilities and metallic features of TMNxO4-x-HTP. The interaction strength between intermediates and catalysts governs the catalytic activities, which can be modulated by tuning the TM atom and the local coordination number of N/O in catalysts. RhN3O1-HTP is an efficient bifunctional catalyst for HER and OER, and RhN1O3-HTP is a promising bifunctional catalyst for OER and ORR. Our findings highlight a potentially efficient class of electrocatalysts based on 2D MOF materials.