Reactive Intermediates Research Articles

Unveiling the Promotion of Sulfides Heterostructure on the Urea Oxidation Reaction: Role of Interface Engineering and Sulfate Adsorption.

The pursuit of efficient and stable urea oxidation reaction (UOR) electrocatalysts is paramount for the sustainable utilization of renewable energy sources and the treatment of wastewater with urea content. This research introduces the successful fabrication of (Fe0.5Ni0.5)0.96S/Co9S8/NF mesh heterojunction materials, which are replete with interfaces that facilitate enhanced catalytic activity. Benefiting from the electron transfer behavior from (Fe0.5Ni0.5)0.96S to Co9S8, and the promotion of surface adsorption of SO4 2-, the (Fe0.5Ni0.5)0.96S/Co9S8/NF electrocatalyst has excellent UOR catalytic performance. The experimental characterization and theoretical simulation show that the d-band center/thermodynamic barrier of (Fe0.5Ni0.5)0.96S/Co9S8/NF is regulated by the redistribution of electrons at the heterojunction interface, and the adsorption of SO4 2- on the surface. The reaction barrier of the adsorption strength/rate-controlling step of urea and reaction intermediates is optimized, which promotes the catalytic kinetics and thermodynamics of UOR, offering a promising strategy for advancing energy and environmental technologies.

Selective peptide bond formation via side chain reactivity and self-assembly of abiotic phosphates

In the realm of biology, peptide bonds are formed via reactive phosphate-containing intermediates, facilitated by compartmentalized environments that ensure precise coupling and folding. Herein, we use aminoacyl phosphate esters, synthetic counterparts of biological aminoacyl adenylates, that drive selective peptide bond formation through side chain-controlled reactivity and self-assembly. This strategy results in the preferential incorporation of positively charged amino acids from mixtures containing natural and non-natural amino acids during the spontaneous formation of amide bonds in water. Conversely, aminoacyl phosphate esters that lack assembly and exhibit fast reactivity result in random peptide coupling. By introducing structural modifications to the phosphate esters (ethyl vs. phenyl) while retaining aggregation, we are able to tune the selectivity by incorporating aromatic amino acid residues. This approach enables the synthesis of sequences tailored to the specific phosphate esters, overcoming limitations posed by certain amino acid combinations. Furthermore, we demonstrate that a balance between electrostatic and aromatic stacking interactions facilitates covalent self-sorting or co-assembly during oligomerization reactions using unprotected N-terminus aminoacyl phosphate esters. These findings suggest that self-assembly of abiotic aminoacyl phosphate esters can activate a selection mechanism enabling the departure from randomness during the autonomous formation of amide bonds in water.

Resolution of Selectivity Steps of CO Reduction Reaction on Copper by Quantum Monte Carlo.

Electrochemical reduction of carbon monoxide to valuable fuels and chemicals on copper surfaces remains a challenging area in catalysis due to a limited understanding of adsorption mechanisms and reaction pathways. Although density functional theory (DFT)-based studies have investigated these processes, their accuracy varies across different functionals. Here, we present the application of fixed-node diffusion Monte Carlo (FNDMC) to benchmark the adsorption energies of CO*, H*, and key CO reduction reaction (CORR) intermediates, COH* and CHO* on the Cu(111) surface. Our results for CO* and H* adsorption energies closely align with experimentally measured chemisorption reactions, highlighting the limitations of DFT and providing site-specific energy comparisons that are often not available experimentally. Additionally, we explore the effect of explicit solvation, demonstrating how water stabilizes the COH* over CHO*, thus suggesting a critical role of COH* in CORR. Finally, we release our high-accuracy FNDMC benchmarks for testing and developing new DFT functionals for electrocatalysis. Overall, this study underscores the potential of FNDMC for detailed surface chemistry studies and offers new insights into catalytic processes.

Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites

The universal linear scaling relationships between the adsorption energies of reactive intermediates limit the performance of catalysts in multi-step catalytic reactions. Here, we show how these scaling relationships can be circumvented in electrochemical oxygen evolution reaction by dynamic structural regulation of active sites. We construct a model Ni-Fe2 molecular catalyst via in situ electrochemical activation, which is able to deliver a notable intrinsic oxygen evolution reaction activity. Theoretical calculations and electrokinetic studies reveal that the dynamic evolution of Ni-adsorbate coordination driven by intramolecular proton transfer can effectively alter the electronic structure of the adjacent Fe active centre during the catalytic cycle. This dynamic dual-site cooperation simultaneously lowers the free energy change associated with O–H bond cleavage and O–O bond formation, thereby disrupting the inherent scaling relationship in oxygen evolution reaction. The present study not only advances the development of molecular water oxidation catalysts, but also provides an unconventional paradigm for breaking the linear scaling relationships in multi-intermediates involved catalysis.

Bis-Cycloruthenated Complexes in Visible Light-Induced C-H Alkylation with Epoxides.

Bis-cycloruthenated complexes (BCRCs) of the type [Ru(N^C)2L2] are proposed to be key reactive intermediates in the Ru(II)-catalyzed directed C-H functionalization of arenes. While the exceptional ground state reactivity of BCRCs toward a number of electrophiles has been explored, their reactivity upon photoexcitation is still unknown. Herein, we report studies on the photoexcitation of BCRCs that establish their capability to access chemically useful excited states. Remarkably, photoexcited BCRCs demonstrate greatly increased reactivity toward the electron transfer processes required for alkyl halide activation, overcoming current limitations of their ground-state reactivity. We have demonstrated this reactivity by expanding upon the current chemical space occupied by Ru-catalyzed C-H functionalization to include ortho-alkylation with epoxides.

Discovery of iron-oxo-catalyzed oxidation of fluorophenyl systems to carbonyls or epoxides: reactive intermediates determined mechanism.

Carbonyl and epoxide compounds play crucial roles in organic synthesis, and the utilization of metal catalysis offers distinct advantages. However, the catalysis of their synthesis by high-valent iron-oxo remains a challenge. In this study, we investigated iron-oxo-catalyzed phenyl systems in detail. Our results show that the carbon atoms on the aromatic ring are positively charged by replacing a hydrogen atom with a fluorine atom, which leads to different catalytic mechanisms. Specifically, the cationic intermediate formed via a double-electron transfer in the low-spin (LS) state of a non-fluorinated benzene ring transforms into a radical intermediate via single-electron transfer when fluorine substitution occurs. Further computational investigations revealed that different intermediates in LS drive the formation of different products. The carbocation intermediate strongly favors the generation of carbonyl compounds through the migration of the ipso - hydrogen (known as the "NIH shift"). In contrast, the radical intermediate exhibits kinetic advantages in this pathway, leading to the formation of epoxides. This research provides theoretical support and facilitates the exploration of innovative pathways for carbonyl and epoxide synthesis. Computing was performed via Gaussian 09 software. Geometric optimization, transition state search, and intrinsic reaction coordinate (IRC) analysis were conducted via the hybrid functional B3LYP and the 6-311G(d,p) basis set. Single-point energy calculations were performed via a higher-level basis set, def2-TZVP. Multiwfn 8.0 and VMD 1.9.1 software are utilized for spin density and molecular frontier orbital analysis, as well as for graphically representing key intermediates.

Industrial-level Paired Electrosynthesis of Valuable Chemicals over a High-performance Heterostructural Electrode.

Paired electrosynthetic technology is of significance to realize the co-production of high-added value chemicals. However, exploiting efficient bifunctional electrocatalyst of the concurrent electrocatalysis to achieve the industrial-level performance is still challenging. Herein, an amorphous Co2P@MoOx heterostructure is rationally designed by in-situ electrodeposition strategy, which is acted as excellent bifunctional catalysts for the electrocatalytic nitrite reduction reaction (NO2RR) and glycerol oxidation reaction (GOR). The membrane-electrode assembly (MEA) electrolyzer realizes a low voltage of 1.30 V, robust stability over 200 h at 100 mA cm-2, high Faraday efficiencies and yield of NH3 (above 95%, 49.7 mg h-1 cm-2) and formate (above 95%, 152.3 mg h-1 cm-2) at industrial-level current density of 500 mA cm-2. In-situ spectroscopy studies have shown that high-valence CoOOH is the main active material of GOR, and the main catalytic conversion pathway of NO2RR involves key *NH2OH reaction intermediates. In addition, theoretical calculations confirm that the Co2P@MoOx heterostructure has strong interfacial electronic interaction and optimized reaction energy barriers, which endows its intrinsically high electrocatalytic activity for the co-electrosynthesis of NH3 and formate.

Industrial‐level Paired Electrosynthesis of Valuable Chemicals over a High‐performance Heterostructural Electrode

Paired electrosynthetic technology is of significance to realize the co‐production of high‐added value chemicals. However, exploiting efficient bifunctional electrocatalyst of the concurrent electrocatalysis to achieve the industrial‐level performance is still challenging. Herein, an amorphous Co2P@MoOx heterostructure is rationally designed by in‐situ electrodeposition strategy, which is acted as excellent bifunctional catalysts for the electrocatalytic nitrite reduction reaction (NO2RR) and glycerol oxidation reaction (GOR). The membrane‐electrode assembly (MEA) electrolyzer realizes a low voltage of 1.30 V, robust stability over 200 h at 100 mA cm‐2, high Faraday efficiencies and yield of NH3 (above 95%, 49.7 mg h‐1 cm‐2) and formate (above 95%, 152.3 mg h‐1 cm‐2) at industrial‐level current density of 500 mA cm‐2. In‐situ spectroscopy studies have shown that high‐valence CoOOH is the main active material of GOR, and the main catalytic conversion pathway of NO2RR involves key *NH2OH reaction intermediates. In addition, theoretical calculations confirm that the Co2P@MoOx heterostructure has strong interfacial electronic interaction and optimized reaction energy barriers, which endows its intrinsically high electrocatalytic activity for the co‐electrosynthesis of NH3 and formate.

Structural investigations of the benzoyl fluoride and the benzoacyl cation of low-melting compounds and reactive intermediates.

Acyl fluorides and acyl cations represent typical reactive intermediates in organic reactions, such as Friedel-Crafts acylation. However, the comparatively stable phenyl-substituted compounds have not been fully characterized yet, offering a promising backbone. Attempts to isolate the benzoacylium cation have only been carried out starting from the acyl chloride with weaker chloride-based Lewis acids. Therefore, only adducts of 1,4-stabilized acyl cations could be obtained. Due to the low melting point of benzoyl fluoride, together with its volitality and sensitivity toward hydrolysis, the structures of the acyl fluoride and its acylium cation have not been determined. Herein, we report the first crystal structure of benzoyl fluoride, C7H5FO or PhCOF (monoclinic P21/n, Z = 8) and the benzoacylium undecafluorodiarsenate, C7H5O+·As2F11- or [PhCO]+[As2F11]- (monoclinic P21/n, Z = 4). The compounds were characterized by low-temperature vibrational spectroscopy and single-crystal X-ray analysis, and are discussed together with quantum chemical calculations. In addition, their specific π-interactions were elucidated.

Dirhodium-Catalyzed Asymmetric Transformations of Alkynes via Carbene Intermediates.

ConspectusFunctionalization of alkynes is an established cornerstone of organic synthesis. While numerous transition metals exhibit promising activities in the transformations of alkynes via π-insertion or oxidative cyclometalation, Lewis π-acids offer a different approach. By coordinating with alkynes through π-bonding, Lewis π-acids facilitate nucleophilic addition, leading to the formation of alkenyl metal species. These species can undergo electron rearrangement to generate metal carbenes, which are crucial intermediates for subsequent carbene transfer reactions. This reaction pathway provides a versatile route for alkyne functionalization, especially in an asymmetric manner. Although the Lewis π-acid, gold(I), pioneered this reaction mode, the development of asymmetric variants remains challenging due to the linear coordination of gold(I). Therefore, expanding the range of catalysts beyond gold(I) complexes to other metal catalysts would facilitate further advances in chiral molecule construction and the exploration of novel reaction modes.In this Account, we present a concise review of alkyne multifunctionalization via dirhodium-catalyzed asymmetric transformations, providing the development of the modulation strategies and substrates and plausible reaction mechanisms. In the aromatization-driven strategy, the furanyl dirhodium carbene is generated from an enynone, which is terminated by enantioselective intramolecular C-H insertion, cyclopropanation, aromatic substitution, or the Büchner reaction, giving chiral dihydroindoles, dihydrobenzofurans, cyclopropane-fused tetrahydroquinolines, fluorenes, or cyclohepta[b]benzofurans. The cap-tether modulation strategy was developed in a subsequent study to balance the reactivity and selectivity of an azo-enyne. This strategy gave the first catalytic asymmetric cycloisomerization of azo-enyne, affording centrally and axially chiral isoindazole derivatives. The synergistic activation strategy, i.e., EWG activation and C-H···O interaction, was introduced to achieve the first dirhodium-catalyzed asymmetric cycloisomerization of enynes, providing a range of chiral cyclopropane-annulated bicyclic systems from enynals. Benefiting from these successes, difluoromethyl-substituted enynes were designed and proven to be effective substrates. With the corresponding benzo-1,6-enynes as the substrates, the enantioselective biscyclopropanation and the cascaded cyclopropanation/cyclopropenation were achieved using alkynes as dicarbene equivalents. Additionally, benzo-1,5-enynal generated vinyl dirhodium carbene, which reacted with a variety of alkenes via [2 + 1] cycloaddition, [4 + 3] cycloaddition, or formal allylation, giving spiro and fused polycyclic heterocycles. Coupling the synergistic activation strategy with desymmetrization, we further successfully achieved the asymmetric cycloisomerization of diynals, constructing furan-fused dihydropiperidines with an alkyne-substituted aza-quaternary stereocenter. Notably, by analyzing X-ray structures of several dirhodium-alkyne π-complexes, together with the results of DFT calculations and control experiments, we obtained evidence supporting the synergistic activation mode, making the well-defined paddlewheel-like dirhodium(II) stand out among the other metal complexes. We anticipate that our research will significantly advance the fields of dirhodium, alkyne, and carbene chemistry.

Advanced Zeolite-based Catalysts for CO2 Hydrogenation to Targeted High-Value Chemicals and Fuels.

The excessive use of fossil fuels has resulted in elevated CO2 emissions in the atmosphere, significantly impacting the climate and global environment. The catalytic conversion of CO2 into high-value chemicals has been recognized as a promising strategy to mitigate CO2 emissions. Light olefins, aromatics, and alcohols, etc. are widely used high-value chemicals as fuels and chemical synthesis intermediates. To enhance the catalytic efficiency and selectivity for producing these chemicals, various catalysts have been developed. Among them, zeolite-based catalysts have garnered significant attention due to their unique microporous structure, shape-selective catalysis capability, high thermal stability, and tunable acidity. This article focuses on the distinctive structural characteristics of zeolites and their notable representative applications, with particular emphasis on the impact of zeolite structural properties on catalytic performance and reaction mechanism. Additionally, we discuss the current challenges of fabricating highly efficient zeolite-based catalysts and future development prospects in improving the catalytic performance and industrial-scale applications. We propose rational and strategic insights to pave the way for the efficient utilization of CO₂ as a valuable resource.

Transient pulsed discharge preparation of graphene aerogel supports asymmetric Cu cluster catalysts promote CO2 electroreduction

Designing asymmetrical structures is an effective strategy to optimize metallic catalysts for electrochemical carbon dioxide reduction reactions. Herein, we demonstrate a transient pulsed discharge method for instantaneously constructing graphene-aerogel supports asymmetric copper nanocluster catalysts. This process induces the convergence of copper atoms decomposed by copper chloride onto graphene originating from the intense current pulse and high temperature. The catalysts exhibit asymmetrical atomic and electronic structures due to lattice distortion and oxygen doping of copper clusters. In carbon dioxide reduction reaction, the selectivity and activity for ethanol production are enhanced by the asymmetric structure and abundance of active sites on catalysts, achieving a Faradaic efficiency of 75.3% for ethanol and 90.5% for multicarbon products at −1.1 V vs. reversible hydrogen electrode. Moreover, the strong interactions between copper nanoclusters and graphene-aerogel support confer notable long-term stability. We elucidate the key reaction intermediates and mechanisms on Cu4O-Cu/C2O1 moieties through in situ testing and density functional theory calculations. This study provides an innovative approach to balancing activity and stability in asymmetric-structure catalysts for energy conversion.

Conformational dynamics of a multienzyme complex in anaerobic carbon fixation.

In the ancient microbial Wood-Ljungdahl pathway, carbon dioxide (CO2) is fixed in a multistep process that ends with acetyl-coenzyme A (acetyl-CoA) synthesis at the bifunctional carbon monoxide dehydrogenase/acetyl-CoA synthase complex (CODH/ACS). In this work, we present structural snapshots of the CODH/ACS from the gas-converting acetogen Clostridium autoethanogenum, characterizing the molecular choreography of the overall reaction, including electron transfer to the CODH for CO2 reduction, methyl transfer from the corrinoid iron-sulfur protein (CoFeSP) partner to the ACS active site, and acetyl-CoA production. Unlike CODH, the multidomain ACS undergoes large conformational changes to form an internal connection to the CODH active site, accommodate the CoFeSP for methyl transfer, and protect the reaction intermediates. Altogether, the structures allow us to draw a detailed reaction mechanism of this enzyme, which is crucial for CO2 fixation in anaerobic organisms.

Designing Supported Nanoparticles via Synergistic Ex-Solution and Phosphorization for Tailored Active Site Generation.

Supported nanoparticles incorporating catalytically attractive nonmetal elements have gained significant attention as a promising strategy for enhancing catalytic activity in various industrial applications. This study presents an innovative one-pot synthesis method for fabricating hybrid catalysts, which simultaneously modifies surface properties through the precipitation of nanoparticles with the concurrent incorporation of nonmetal elements. The underlying concept is to synchronize the temperature required for particle formation with that of nonmetal incorporation by adjusting the oxygen chemical potential of the host oxide. As a case study, Ir- and Ru-doped WO3 are selected as the starting material, with phosphorus (P) as the representative nonmetal for surface functionalization. Notably, the hybrid catalyst, composed of amorphous (Ir,Ru)Px particles dispersed on P-rich WO2.9 sheets, is synthesized through a single heat treatment at 500°C, avoiding undesirable sintering of the host material. When used as a hydrogen evolution catalyst, this material exhibits outstanding mass activity, durability, compared to state-of-the-art Pt/C catalysts. Density functional theory calculations further reveal that the superior performance of the hybrid catalysts attributes to improved water dissociation and favorable adsorption and desorption of key reaction intermediates. This novel synthesis strategy offers considerable potential for advancing diverse areas of heterogeneous catalysis.

Electrochemically Driven Selective Olefin Epoxidation by Cobalt-TAML Catalyst.

Epoxides are versatile chemical intermediates that are used in the manufacture of diversified industrial products. For decades, thermochemical conversion has long been employed as the primary synthetic route. However, it has several drawbacks, such as harsh and explosive operating conditions, as well as a significant greenhouse gas emissions problem. In this study, we propose an alternative electrocatalytic epoxidation reaction, using [CoIII(TAML)]- (TAML = tetraamido macrocyclic ligand) as a molecular catalyst. Under ambient conditions, the catalyst selectively epoxidized olefin substrates using water as the oxygen atom source, affording an efficient catalytic epoxidation of olefins with a broad substrate scope. Notably, [CoIII(TAML)]- achieved >60% Faradaic efficiency (FE) with >90% selectivity for cyclohexene epoxidation, which other heterogeneous electrocatalysts have never attained. Electrokinetic studies shed further light on the detailed mechanism of olefin epoxidation, which involved a rate-limiting proton-coupled electron transfer process, forming reactive cobalt oxygen active species embedded in 2e-oxidized TAML. Operando voltammetry-electrospray ionization mass spectrometry (VESI-MS) and electron paramagnetic resonance (EPR) analyses were utilized to identify a cobalt oxygen active intermediate during an electrocatalytic epoxidation by [CoIII(TAML)]-. Our findings offer a new possibility for sustainable chemical feedstock production using electrochemical methods.

Self-assembled Gap-Rich PdMn Nanofibers with High Mass/Electron Transport Highways for Electrocatalytic Reforming of Waste Plastics.

Innovating nanocatalysts with both high intrinsic catalytic activity and high selectivity is crucial for multi-electron reactions, however, their low mass/electron transport at industrial-level currents is often overlooked, which usually leads to low comprehensive performance at the device level. Herein, a Cl-/O2 etching-assisted self-assembly strategy is reported for synthesizing a self-assembled gap-rich PdMn nanofibers with high mass/electron transport highway for greatly enhancing the electrocatalytic reforming of waste plastics at industrial-level currents. The self-assembled PdMn nanofiber shows excellent catalytic activity in upcycling waste plastics into glycolic acid, with a high current density of 223 mA cm-2@0.75 V (vs RHE), high selectivity (95.6%), and Faraday efficiency (94.3%) to glycolic acid in a flow electrolyzer. Density functional theory calculation, X-ray absorption spectroscopy combined with in situ electrochemical Fourier transform infrared spectroscopy reveals that the introduction of highly oxophilic Mn induces a downshift of the d-band center of Pd, which optimizes the adsorption energy of the reaction intermediates on PdMn surface, thereby facilitating the desorption of glycolic acid as a high-value product. Computational fluid dynamics simulations confirm that the gap-rich nanofiber structure is conducive for mass transfer to deliver an industrial-level current.

Boosting OER Performance of NiFe‐MOFs via Heterostructure Engineering: Promoted Phase Transformation and Self‐optimized Dynamic Interface Electron Structure

AbstractHow to manipulate heterostructure engineering to achieve high‐efficiency oxygen evolution reaction (OER) remains a significant challenge. Herein, a promising OER heterostructure electrocatalyst with IrNi nanoalloys (≈3.29 ± 0.12 nm) anchored on NiFe‐MOFs (IrNi@NiFe‐MOFs), exhibiting promoted phase transformation and self‐optimized dynamic interface electronic structure, via a one‐step hydrothermal method is designed and developed. Specifically, IrNi@NiFe‐MOFs displays excellent OER performance with a low overpotential of 228 mV at 10 mA cm−2, a small Tafel slope of 37.6 mV dec−1, and robust stability at 10 and 100 mA cm−2. Experimental and theoretical calculations identify the actual active sites as IrNi@NiFeOOH and further reveal that the dynamic structure evolution and self‐optimized dynamic interface electron structure, promoted by heterostructure engineering, boost its OER catalytic performance. Moreover, IrNi@NiFeOOH heterostructure displays strong interface electron interactions and a unique self‐optimized dynamic interface electron structure, resulting in better charge redistribution and adaptive bonding (Ir─O─Ni/Fe bonds). This structure therefore plays a critical role in promoting electron transfer, facilitating the dynamic evolution of reaction intermediates, and reducing the energy barrier of the potential‐determining step, thereby boosting the OER performance. These findings provide new insights into the development of MOF‐based electrocatalysts via heterostructure engineering.

Recent Advances in Transition Metal Chalcogenides Electrocatalysts for Oxygen Evolution Reaction in Water Splitting

Rapid industrial growth has overexploited fossil fuels, making hydrogen energy a crucial research area for its high energy and zero carbon emissions. Water electrolysis is a promising method as it is greenhouse gas-free and energy-efficient. However, OER, a slow multi-electron transfer process, is the limiting step. Thus, developing efficient, low-cost, abundant electrocatalysts is vital for large-scale water electrolysis. In this paper, the application and progress of transition metal chalcogenides (TMCs) as catalysts for the oxygen evolution reaction in recent years are comprehensively reviewed. The key findings highlight the catalytic mechanism and performance of TMCs synthesized using single or multiple transition metals. Notably, modifications through recombination, heterogeneous interface engineering, vacancy, and atom doping are found to effectively regulate the electronic structure of metal chalcogenides, increasing the number of active centers and reducing the adsorption energy of reaction intermediates and energy barriers in OER. The paper further discusses the shortcomings and challenges of TMCs as OER catalysts, including low electrical conductivity, limited active sites, and insufficient stability under harsh conditions. Finally, potential research directions for developing new TMC catalysts with enhanced efficiency and stability are proposed.

Toward Scalable Synthesis of Mo2C/MoNi4 Heterojunction Catalysts on Ni Mesh via Laser Radiation for Efficient H2 Production in Alkaline Electrolysis

AbstractThe alkaline electrolysis is the dominant production method for hydrogen since non‐noble Ni metals can be used as catalysts. The low activity of the commercial nickel mesh (NM) electrodes remains a considerable obstacle to reducing energy consumption for water splitting. Conducting surface modification on commercial NM is a promising tactic to improve the hydrog enevolution reaction (HER) intrinsic activity of NM catalysts. Herein, Mo2C/MoNi4 heterojunction coating on the NM substrate via a laser Radiation strategy is designed. The results indicate that the Mo2C8.5/MoNi4/NM delivers an extremely low overpotential to trigger HER (η10 = 49.5 mV) processes and maintains a stable overpotential for 100 h in alkaline media. The experimental and theoretical calculations reveal that the downshifted d‐band center of Ni in MoNi4 caused by two‐phase heterojunction can regulate the free energy of reactive intermediates adsorption & desorption, thereby accelerating the entire HER process. This work will open up an avenue for developing highly efficient Ni‐based heterostructured electrocatalysts for commercial HER electrode application.

Achieving Near Infrared Photodegradation by the Synergistic Effect of Z-Scheme Heterojunction and Antenna of Rare Earth Single Atoms.

Near-infrared light response catalysts have received great attention in renewable solar energy conversion, energy production, and environmental purification. Here, near-infrared photodegradation is successfully achieved in rare earth single atom anchored NaYF4@g-C3N4 heterojunctions by the synergistic effect of Z-scheme heterojunction and antenna of rare earth single atoms. The UV-vis light emitted by Tm3+ can not only be directly absorbed by g-C3N4 to generate electron-hole pairs, realizing efficient energy transfer, but also be absorbed by NaYF4 substrate, and generating photo-generated electrons at its impurity level, transferring the active charge to the valence band of g-C3N4, forming a Z-scheme heterojunction and further improving the photocatalytic efficiency. Importantly, Tm single atoms has multiple functions such as acting as charge transfer channels to facilitate charge transfer, regulating the critical distance of energy transfer, and prolonging electron-hole pair lifetime. Under NIR light, it exhibited remarkable performance in degrading antibiotics (the removal rate of TC reached 91% for 6 h) while maintaining excellent stability. The LC-MS/MS technology is used to reveal the reaction intermediates, active species, and reaction pathways, and the complex mechanism of photodegradation is further proposed. This study provides experimental and theoretical support for designing and synthesizing catalysts with near-infrared light response characteristics.