Mesoporous Nitrogen‐Doped Carbon‐Nanosphere‐Supported Isolated Single‐Atom Pd Catalyst for Highly Efficient Semihydrogenation of Acetylene

Semihydrogenation of acetylene in the ethylene feed is a vital step for the industrial production of polyethylene. Despite their favorable reaction activity and ethylene selectivity, the Pd‐based intermetallic compound and single‐atom alloy catalysts still suffer from the limitation of atomic utilization derived from the partial exposure of active Pd atoms. Herein, a hard‐template Lewis acid doping strategy is reported that can overcome the inefficient utilization of Pd atoms. In this strategy, N‐coordinated isolated single‐atomic Pd sites are fully embedded on the inner walls of mesoporous nitrogen‐doped carbon foam nanospheres (ISA‐Pd/MPNC). This synthetic strategy has been proved to be applicable to prepare other ISA‐M/MPNC (M = Pt and Cu) materials. This ISA‐Pd/MPNC catalyst with both high specific surface area (633.8 m² g^?1) and remarkably thin pore wall (1–2 nm) exhibits higher activity than that of its nonmesoporous counterpart (ISA‐Pd/non‐MPNC) catalyst by a factor of 4. This work presents an efficient way to tailor and optimize the catalytic activity and selectivity by atomic‐scale design and structural control.     

Enhancing both selectivity and coking-resistance of a single-atom Pd<Subscript>1</Subscript>/C<Subscript>3</Subscript>N<Subscript>4</Subscript> catalyst for acetylene hydrogenation

Selective hydrogenation is an important industrial catalytic process in chemical upgrading,where Pd-based catalysts are widely used because of their high hydrogenation activities.However,poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns.In this work,atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride (g-C3N4) using atomic layer deposition.Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle (NP) formation.During selective hydrogenation of acetylene in excess ethylene,the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/A12O3 and Pd/SiO2 catalysts.In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement.More impressively,the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance.Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.     

Co‐Based Catalysts Derived from Layered‐Double‐Hydroxide Nanosheets for the Photothermal Production of Light Olefins

Solar‐driven Fischer–Tropsch synthesis represents an alternative and potentially low‐cost route for the direct production of light olefins from syngas (CO and H₂). Herein, a series of novel Co‐based photothermal catalysts with different chemical compositions are successfully fabricated by H₂ reduction of ZnCoAl‐layered double‐hydroxide nanosheets at 300–700 °C. Under UV–vis irradiation, the photothermal catalyst prepared at 450 °C demonstrates remarkable CO hydrogenation performance, affording an olefin (C_2–4⁼) selectivity of 36.0% and an olefin/paraffin ratio of 6.1 at a CO conversion of 15.4%. Characterization studies using X‐ray absorption fine structure and high‐resolution transmission electron microscopy reveal that the active catalyst comprises Co and Co₃O₄ nanoparticles on a ZnO–Al₂O₃ mixed metal oxide support. Density functional theory calculations further demonstrate that the oxide‐decorated metallic Co nanoparticle heterostructure weakens the further hydrogenation ability of the corresponding Co, leading to the high selectivity to light olefins. This study demonstrates a novel solar‐driven catalyst platform for the production of light olefins via CO hydrogenation.     

Control of Local Electronic Structure of Pd Single Atom Catalyst by Adsorbate Induction

Aiming at regulating and controlling the localized electronic states while maintaining the metal atoms in the isolation form, an in situ adsorbate induced strategy is proposed at a programmed temperature to activate Zr-based metal–organic framework (MOF) supported single Pd atom catalyst. It is discovered that in situ treatment environments trigger the change of lattice parameters in MOF materials by reaction heat effect, observed by in situ X-ray diffraction, spherical aberration-corrected electron microscope, and X-ray adsorption fine structure (XAFS). The as-obtained electron-deficient Pd single atoms are critical to the high intrinsic activity (turnover frequency of 0.132 s^?1) and selectivity of 93% with the long-term stability in the semihydrogenation of acetylene, which can be comparable to the state-of-the-art Pd catalysts. This superior catalytic behavior correlates with the reduced C₂H₄ desorption energy and the activation barriers for the hydrogenation, confirmed by density functional theory calculation.     

Alumina‐Supported CoFe Alloy Catalysts Derived from Layered‐Double‐Hydroxide Nanosheets for Efficient Photothermal CO2 Hydrogenation to Hydrocarbons

A series of novel CoFe‐based catalysts are successfully fabricated by hydrogen reduction of CoFeAl layered‐double‐hydroxide (LDH) nanosheets at 300–700 °C. The chemical composition and morphology of the reaction products (denoted herein as CoFe‐x) are highly dependent on the reduction temperature (x). CO₂ hydrogenation experiments are conducted on the CoFe‐x catalysts under UV–vis excitation. With increasing LDH‐nanosheet reduction temperature, the CoFe‐x catalysts show a progressive selectivity shift from CO to CH₄, and eventually to high‐value hydrocarbons (C₂₊). CoFe‐650 shows remarkable selectivity toward hydrocarbons (60% CH₄, 35% C₂₊). X‐ray absorption fine structure, high‐resolution transmission electron microscopy, Mössbauer spectroscopy, and density functional theory calculations demonstrate that alumina‐supported CoFe‐alloy nanoparticles are responsible for the high selectivity of CoFe‐650 for C₂₊ hydrocarbons, also allowing exploitation of photothermal effects. This study demonstrates a vibrant new catalyst platform for harnessing clean, abundant solar‐energy to produce valuable chemicals and fuels from CO₂.     

Metal‐Tuned Acetylene Linkages in Hydrogen Substituted Graphdiyne Boosting the Electrochemical Oxygen Reduction

Different from graphene with the highly stable sp²‐hybridized carbon atoms, which shows poor controllability for constructing strong interactions between graphene and guest metal, graphdiyne has a great potential to be engineered because its high‐reactive acetylene linkages can effectively chelate metal atoms. Herein, a hydrogen‐substituted graphdiyne (HsGDY) supported metal catalyst system through in situ growth of Cu₃Pd nanoalloys on HsGDY surface is developed. Benefiting from the strong metal‐chelating ability of acetylenic linkages, Cu₃Pd nanoalloys are intimately anchored on HsGDY surface that accordingly creates a strong interaction. The optimal HsGDY‐supported Cu₃Pd catalyst (HsGDY/Cu₃Pd‐750) exhibits outstanding electrocatalytic activity for the oxygen reduction reaction (ORR) with an admirable half‐wave potential (0.870 V), an impressive kinetic current density at 0.75 V (57.7 mA cm^?2) and long‐term stability, far outperforming those of the state‐of‐the‐art Pt/C catalyst (0.859 V and 15.8 mA cm^?2). This excellent performance is further highlighted by the Zn–air battery using HsGDY/Cu₃Pd‐750 as cathode. Density function theory calculations show that such electrocatalytic performance is attributed to the strong interaction between Cu₃Pd and C?C bonds of HsGDY, which causes the asymmetric electron distribution on two carbon atoms of C?C bond and the strong charge transfer to weaken the shoulder‐to‐shoulder π conjugation, eventually facilitating the ORR process.     

Anchoring and Upgrading Ultrafine NiPd on Room‐Temperature‐Synthesized Bifunctional NH2‐N‐rGO toward Low‐Cost and Highly Efficient Catalysts for Selective Formic Acid Dehydrogenation

Hydrogen is widely considered to be a sustainable and clean energy alternative to the use of fossil fuels in the future. Its high hydrogen content, nontoxicity, and liquid state at room temperature make formic acid a promising hydrogen carrier. Designing highly efficient and low‐cost heterogeneous catalysts is a major challenge for realizing the practical application of formic acid in the fuel‐cell‐based hydrogen economy. Herein, a simple but effective and rapid strategy is proposed, which demonstrates the synthesis of NiPd bimetallic ultrafine particles (UPs) supported on NH₂‐functionalized and N‐doped reduced graphene oxide (NH₂‐N‐rGO) at room temperature. The introduction of the ? NH₂? N group to rGO is the key reason for the formation of the ultrafine and well‐dispersed Ni_0.4Pd_0.6 UPs (1.8 nm) with relatively large surface area and more active sites. Surprisingly, the as‐prepared low‐cost NiPd/NH₂‐N‐rGO dsiplays excellent hydrophilicity, 100% H₂ selectivity, 100% conversion, and remarkable catalytic activity (up to 954.3 mol H₂ (mol catalyst)^?1 h^?1) for FA decomposition at room temperature even with no additive, which is much higher than that of the best catalysts so far reported.     

Promoting the Direct H2O2 Generation Catalysis by Using Hollow Pd–Sn Intermetallic Nanoparticles

Although direct hydrogen (H₂) oxidation to hydrogen peroxide (H₂O₂) is considered as a promising strategy for direct H₂O₂ synthesis, the desirable conversion efficiency remains formidable challenge. Herein, highly active and selective direct H₂ oxidation to H₂O₂ is achieved by using hollow Pd–Sn intermetallic nanoparticles (NPs) as the catalysts. By tuning the catalytic solvents and catalyst supports, the efficiency of direct H₂ oxidation to H₂O₂ can be optimized well with the hollow Pd₂Sn NPs/P25 exhibiting H₂O₂ selectivity up to 80.7% and productivity of 60.8 mol kg_cat^?1 h^?1. In situ diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption results confirm the different surface atom arrangements between solid and hollow Pd–Sn NPs. X‐ray photoelectron spectra results show that the higher efficiency of Pd₂Sn NPs/P25 is due to its higher content of metallic Pd and higher ratio of Sn^x+, which benefit H₂O₂ production and selectivity.     

Metal–Organic Framework‐Derived Bamboo‐like Nitrogen‐Doped Graphene Tubes as an Active Matrix for Hybrid Oxygen‐Reduction Electrocatalysts

In this work, large size (i.e., diameter > 100 nm) graphene tubes with nitrogen‐doping are prepared through a high‐temperature graphitization process of dicyandiamide (DCDA) and Iron(II) acetate templated by a novel metal–organic framework (MIL‐100(Fe)). The nitrogen‐doped graphene tube (N‐GT)‐rich iron‐nitrogen‐carbon (Fe‐N‐C) catalysts exhibit inherently high activity towards the oxygen reduction reaction (ORR) in more challenging acidic media. Furthermore, aiming to improve the activity and stability of conventional Pt catalysts, the ORR active N‐GT is used as a matrix to disperse Pt nanoparticles in order to build a unique hybrid Pt cathode catalyst. This is the first demonstration of the integration of a highly active Fe‐N‐C catalyst with Pt nanoparticles. The synthesized 20% Pt/N‐GT composite catalysts demonstrate significantly enhanced ORR activity and H₂‐air fuel cell performance relative to those of 20% Pt/C, which is mainly attributed to the intrinsically active N‐GT matrix along with possible synergistic effects between the non‐precious metal active sites and the Pt nanoparticles. Unlike traditional Pt/C, the hybrid catalysts exhibit excellent stability during the accelerated durability testing, likely due to the unique highly graphitized graphene tube morphologies, capable of providing strong interaction with Pt nanoparticles and then preventing their agglomeration.     

Liquid-phase selective hydrogenation of phenol to cyclohexanone over the Ce-doped Pd-B amorphous alloy catalyst

Ce-doped Pd-B amorphous alloy catalysts were prepared by chemical reduction of mixed PdCl₂ and Ce(NO₃)₃ with KBH₄. During liquid-phase selective hydrogenation of phenol to cyclohexanone, the as-prepared Pd-Ce-B catalysts exhibited much higher activity, better selectivity and excellent durability than the undoped Pd-B. Based on various characterizations, the promoting effect of Ce-dopant on the catalytic properties can be addressed as follows: (1) stabilizing the amorphous structure of Pd-B alloy and enhancing the dispersion degree of Pd active sites; (2) increasing the electron density of Pd, which could enhance hydrogenation activity and improve catalytic durability; (3) increasing the surface basicity, which facilitated the non-planar adsorption of phenol on catalyst surface, leading to higher cyclohexanone selectivity.     

Single‐Atom Nanozyme Based on Nanoengineered Fe–N–C Catalyst with Superior Peroxidase‐Like Activity for Ultrasensitive Bioassays

Single‐atom catalysts are becoming a hot research topic owing to their unique characteristics of maximum specific activity and atomic utilization. Herein, a new single‐atom nanozyme (SAN) based on single Fe atoms anchored on N‐doped carbons supported on carbon nanotube (CNT/FeNC) is proposed. The CNT/FeNC with robust atomic Fe–N_x moieties is synthesised, showing superior peroxidase‐like activity. Furthermore, the CNT/FeNC is used as the signal element in a series of paper‐based bioassays for ultrasensitive detection of H₂O₂, glucose, and ascorbic acid. The SAN provides a new type of signal element for developing various biosensing techniques.     

Promoting Effect of Ni(OH)2 on Palladium Nanocrystals Leads to Greatly Improved Operation Durability for Electrocatalytic Ethanol Oxidation in Alkaline Solution

Most electrocatalysts for the ethanol oxidation reaction suffer from extremely limited operational durability and poor selectivity toward the C?C bond cleavage. In spite of tremendous efforts over the past several decades, little progress has been made in this regard. This study reports the remarkable promoting effect of Ni(OH)₂ on Pd nanocrystals for electrocatalytic ethanol oxidation reaction in alkaline solution. A hybrid electrocatalyst consisting of intimately mixed nanosized Pd particles, defective Ni(OH)₂ nanoflakes, and a graphene support is prepared via a two‐step solution method. The optimal product exhibits a high mass‐specific peak current of >1500 mA mg^?1_Pd, and excellent operational durability forms both cycling and chronoamperometric measurements in alkaline solution. Most impressively, this hybrid catalyst retains a mass‐specific current of 440 mA mg^?1 even after 20 000 s of chronoamperometric testing, and its original activity can be regenerated via simple cyclic voltammetry cycles in clean KOH. This great catalyst durability is understood based on both CO stripping and in situ attenuated total reflection infrared experiments suggesting that the presence of Ni(OH)₂ alleviates the poisoning of Pd nanocrystals by carbonaceous intermediates. The incorporation of Ni(OH)₂ also markedly shifts the reaction selectivity from the originally predominant C2 pathway toward the more desirable C1 pathway, even at room temperature.     

Atomic Fe Dispersed on N‐Doped Carbon Hollow Nanospheres for High‐Efficiency Electrocatalytic Oxygen Reduction

Exploration of high‐efficiency, economical, and ultrastable electrocatalysts for the oxygen reduction reaction (ORR) to substitute precious Pt is of great significance in electrochemical energy conversion devices. Single‐atom catalysts (SACs) have sparked tremendous interest for their maximum atom‐utilization efficiency and fascinating properties. Therefore, the development of effective synthetic methodology toward SACs becomes highly imperative yet still remains greatly challenging. Herein, a reliable SiO₂‐templated strategy is elaborately designed to synthesize atomically dispersed Fe atoms anchored on N‐doped carbon nanospheres (denoted as Fe–N–C HNSs) using the cheap and sustainable biomaterial of histidine (His) as the N and C precursor. By virtue of the numerous atomically dispersed Fe–N₄ moieties and unique spherical hollow architecture, the as‐fabricated Fe–N–C HNSs exhibit excellent ORR performance in alkaline medium with outstanding activity, high long‐term stability, and superior tolerance to methanol crossover, exceeding the commercial Pt/C catalyst and most previously reported non‐precious‐metal catalysts. This present synthetic strategy will provide new inspiration to the fabrication of various high‐efficiency single‐atom catalysts for diverse applications.     

Selective hydrogenation of acetylene over egg-shell palladium nano-catalyst

A novel egg-shell Pd/PHSNs nano-catalyst was prepared by a wet impregnation method using self-synthesized porous hollow silica nanoparticles (PHSNs) as support and applied in selective hydrogenation of acetylene to remove acetylene from the ethylene feed. By controlling the preparing conditions and calcining temperature, the active metal particles were loaded evenly on the support with a size about 5 nm. Compared with conventional catalysts prepared with solid silica nanoparticles, solid Al2O3 millispheres and a commercial catalyst, the Pd/PHSNs catalyst showed higher acetylene conversion rates at same reaction temperatures, and the porous hollow nano structure of PHSNs allowed smoother diffusion of ethylene molecules within the catalyst matrix so that ethylene could migrate away from the active sites in time to avoid turning into ethane, which resulted in superior ethylene selectivity at high acetylene conversion rates.     

Oxidase‐Like Fe‐N‐C Single‐Atom Nanozymes for the Detection of Acetylcholinesterase Activity

Single‐atom catalysts (SACs) have attracted extensive attention in the catalysis field because of their remarkable catalytic activity, gratifying stability, excellent selectivity, and 100% atom utilization. With atomically dispersed metal active sites, Fe‐N‐C SACs can mimic oxidase by activating O₂ into reactive oxygen species, O₂^?? radicals. Taking advantages of this property, single‐atom nanozymes (SAzymes) can become a great impetus to develop novel biosensors. Herein, the performance of Fe‐N‐C SACs as oxidase‐like nanozymes is explored. Besides, the Fe‐N‐C SAzymes are applied in biosensor areas to evaluate the activity of acetylcholinesterase based on the inhibition toward nanozyme activity by thiols. Moreover, this SAzymes‐based biosensor is further used for monitoring the amounts of organophosphorus compounds.     

C3N—A 2D Crystalline,Hole‐Free,Tunable‐Narrow‐Bandgap Semiconductor with Ferromagnetic Properties

Graphene has initiated intensive research efforts on 2D crystalline materials due to its extraordinary set of properties and the resulting host of possible applications. Here the authors report on the controllable large‐scale synthesis of C₃N, a 2D crystalline, hole‐free extension of graphene, its structural characterization, and some of its unique properties. C₃N is fabricated by polymerization of 2,3‐diaminophenazine. It consists of a 2D honeycomb lattice with a homogeneous distribution of nitrogen atoms, where both N and C atoms show a D_6h‐symmetry. C₃N is a semiconductor with an indirect bandgap of 0.39 eV that can be tuned to cover the entire visible range by fabrication of quantum dots with different diameters. Back‐gated field‐effect transistors made of single‐layer C₃N display an on–off current ratio reaching 5.5 × 10¹⁰. Surprisingly, C₃N exhibits a ferromagnetic order at low temperatures (<96 K) when doped with hydrogen. This new member of the graphene family opens the door for both fundamental basic research and possible future applications.     

Iron‐Free Cathode Catalysts for Proton‐Exchange‐Membrane Fuel Cells: Cobalt Catalysts and the Peroxide Mitigation Approach

High‐performance and inexpensive platinum‐group‐metal (PGM)‐free catalysts for the oxygen reduction reaction (ORR) in challenging acidic media are crucial for proton‐exchange‐membrane fuel cells (PEMFCs). Catalysts based on Fe and N codoped carbon (Fe–N–C) have demonstrated promising activity and stability. However, a serious concern is the Fenton reactions between Fe²⁺ and H₂O₂ generating active free radicals, which likely cause degradation of the catalysts, organic ionomers within electrodes, and polymer membranes used in PEMFCs. Alternatively, Co–N–C catalysts with mitigated Fenton reactions have been explored as a promising replacement for Fe and PGM catalysts. Therefore, herein, the focus is on Co–N–C catalysts for the ORR relevant to PEMFC applications. Catalyst synthesis, structure/morphology, activity and stability improvement, and reaction mechanisms are discussed in detail. Combining experimental and theoretical understanding, the aim is to elucidate the structure–property correlations and provide guidance for rational design of advanced Co catalysts with a special emphasis on atomically dispersed single‐metal‐site catalysts. In the meantime, to reduce H₂O₂ generation during the ORR on the Co catalysts, potential strategies are outlined to minimize the detrimental effect on fuel cell durability.     

High‐Efficient,Stable Electrocatalytic Hydrogen Evolution in Acid Media by Amorphous FexP Coating Fe2N Supported on Reduced Graphene Oxide

Development of efficient and durable non‐Pt catalysts for hydrogen evolution reaction (HER) in acid media is highly desirable. Iron nitride has emerged as a promising catalyst for its cost‐effective nature, but the corresponding acidic stability must be promoted. Herein, phosphorus‐decorated Fe₂N and reduced graphene oxide (P‐Fe₂N/rGO) composite are designed and synthesized. X‐ray photoelectron spectroscopy and X‐ray absorption fine structure (XAFS) show that a thin layer amorphous iron phosphide is coated on the surface of Fe₂N nanoparticles, which could be responsible for the well resistance of chemical corrosion in acidic media. Meanwhile, the P‐decoration could tune the electronic state and coordination environment of iron atom as evidenced by XAFS, resulting in dramatically enhanced electrocatalytic activity of P‐Fe₂N/rGO. Density functional theory calculations reveal that both the P‐connected N atoms and the Fe atoms in P‐Fe₂N/rGO catalyst are the main active sites for H* adsorption. The hydrogen‐binding free energy |ΔG_H*| value is close to zero for P‐Fe₂N/rGO, suggesting a good balance between the Volmer and Heyrovsky/Tafel steps in HER kinetics. As expected, P‐Fe₂N/rGO catalyst could achieve a low η_onset of 22.4 mV, a small Tafel plot of 48.7 mV dec^?1, and remarkable stability for HER in acid electrolyte.     

Effect of palladium precursor and preparation method on the catalytic performance of Pd/SiO2 catalysts for benzene hydrogenation

Supported Pd catalysts on silica were prepared by different synthesis methods using Pd(Ac)₂ and PdCl₂ as salts precursors. The obtained materials were characterized by X-Ray Diffraction (XRD), H₂ chemisorption, and temperature programmed desorption of hydrogen (H₂-TPD). The catalytic performances of these catalysts have been evaluated in the hydrogenation of benzene. The obtained results show that metal dispersion and catalytic activity are strongly dependent on the salts precursor and the method of preparation of the catalyst. The catalysts prepared by hydrazine reduction exhibit higher activity in benzene hydrogenation than that by the polyol reduction method. Moreover, the catalyst prepared with palladium acetate showed higher catalytic activity than those prepared with palladium chloride. The superior catalytic performance of this catalyst in the hydrogenation of benzene was ascribed to a significantly better dispersion of Pd particles on the silica support.     

Morphological and Compositional Design of Pd–Cu Bimetallic Nanocatalysts with Controllable Product Selectivity toward CO2 Electroreduction

Electrochemical conversion of carbon dioxide (electrochemical reduction of carbon dioxide) to value‐added products is a promising way to solve CO₂ emission problems. This paper describes a facile one‐pot approach to synthesize palladium–copper (Pd–Cu) bimetallic catalysts with different structures. Highly efficient performance and tunable product distributions are achieved due to a coordinative function of both enriched low‐coordinated sites and composition effects. The concave rhombic dodecahedral Cu₃Pd (CRD‐Cu₃Pd) decreases the onset potential for methane (CH₄) by 200 mV and shows a sevenfold CH₄ current density at ?1.2 V (vs reversible hydrogen electrode) compared to Cu foil. The flower‐like Pd₃Cu (FL‐Pd₃Cu) exhibits high faradaic efficiency toward CO in a wide potential range from ?0.7 to ?1.3 V, and reaches a fourfold CO current density at ?1.3 V compared to commercial Pd black. Tafel plots and density functional theory calculations suggest that both the introduction of high‐index facets and alloying contribute to the enhanced CH₄ current of CRD‐Cu₃Pd, while the alloy effect is responsible for high CO selectivity of FL‐Pd₃Cu.