Active Cocatalysts Research Articles

One Iron for Two Iron Sites in a Metal-Organic Framework Toward Simultaneous N2-H2 Activation under Mild Conditions.

Iron-based catalysts play an important role in the ammonia industry. As one of the most abundant iron minerals, Fe3O4 containing FeII and FeIII sites is widely distributed in the earth's crust and even on exoplanets, theoretically giving it both economic and catalytic potentials in ammonia synthesis. However, in the absence of specific active co-catalyst and harsh conditions, Fe3O4 is impossible to achieve ammonia synthesis alone. Here, we designed to activate the relatively inert FeII and FeIII sites in Fe3O4 with a third FeIII site inlayed in a coordination framework (MIL-101(Fe)) to achieve the unpresented multi-site collaborative catalysis. In-depth mechanism study confirmed the roles of three different Fe sites in N2 activation, H2 activation, and product transfer, respectively. Efficient N2-H2 activation to NH3 on the Fe3O4-based catalytic system has been achieved at extremely mild conditions. Our research provides a theoretical basis and a new strategy for designing efficient non-noble metal-based ammonia synthesis catalyst with minimized energy consumption.

(Invited) Controlled Synthesis of Cocatalyst-Semiconductor Hybrid Nanomaterials for Photocatalytic Water Splitting

With the escalating global demand for energy, mitigating anthropogenic climate change necessitates the pursuit of carbon-neutral energy sources to diminish reliance on fossil fuels. Utilizing particulate photocatalysts for solar-light-driven water splitting presents a promising and sustainable paradigm for the large-scale production of storable and clean H2 fuel. To improve the solar energy conversion efficiency, coupling the photocatalysts with cocatalysts is a broadly adopted approach not only to facilitate charge separation and transport but also to serve as reaction sites and accelerate water-splitting reactions. Recent breakthroughs in colloidal synthesis enable the fabrication of advanced nanoparticles with precise control over size and composition. Colloidal NPs represent ideal cocatalyst candidates due to their capacity to provide numerous active sites and facilitate uninterrupted light absorption by the semiconductor. Here, we introduce our approach to synthesize cocatalyst-semiconductor hybrids as efficient photocatalysts, including the alloying of platinum group metal nanoparticle cocatalysts and the control of single-atom cocatalyst locations on semiconductor nanoparticles.Platinum group metals exhibit high efficiency as cocatalysts in the hydrogen evolution reaction, attributed to their favorable catalytic and electronic properties. Bimetallic alloy systems, in general, can considerably modulate their electronic structures, resulting in exceptional physicochemical properties surpassing those of their monometallic counterparts. Herein, we synthesized PtRu solid-solution alloy nanoparticles as high-performance H2 evolution reaction cocatalysts. The rational integration of PtRu nanoparticles with Al-doped SrTiO3 photocatalyst through liquid-phase adsorption and successive two-step annealing ensure the uniform deposition of PtRu alloy nanoparticles with a solid-solution structure. The bimetallic synergy between Pt and Ru induces higher electrocatalytic activity for the hydrogen evolution reaction and a superior electron-capturing property than its Pt counterpart. Modification of Al-doped SrTiO3 with PtRu alloy nanoparticles, CrOx, and CoOOH results in efficient photocatalytic overall water-splitting activity with an apparent quantum yield of 65% at 365 nm. This work introduces a framework to elucidate catalytic trends, offering rational design guidance for the development of bimetallic solid-solution nanoparticles as highly active cocatalysts for overall water splitting.Single-atom cocatalysts dispersed on semiconductor materials exhibit outstanding heterogeneous catalytic properties through the interactions between the single atoms and the photocatalyst. The nature of these interactions depends on whether the single atoms are located on the surface or within the interior of the photocatalyst. In this work, the location-selective placement of single atoms is achieved by carefully adjusting experimental procedure. Using CdSe nanoplatelets as a support, applying different Pt precursor complexes, solvent, and workup process resulted in location selective deposition of Pt atoms outside/inside CdSe nanoplatelet support. In photocatalytic hydrogen evolution reaction, the surface-adsorbed single Pt atoms exhibit higher stability than the substituted ones. This study provides a viable strategy for the structurally precise synthesis and design of single-atom catalysts.

Oxidizing Role of Cu Cocatalysts in Unassisted Photocatalytic CO2 Reduction Using p-GaN/Al2O3/Au/Cu Heterostructures.

Photocatalytic CO2 reduction to CO under unassisted (unbiased) conditions was recently demonstrated using heterostructure catalysts that combine p-type GaN with plasmonic Au nanoparticles and Cu nanoparticles as cocatalysts (p-GaN/Al2O3/Au/Cu). Here, we investigate the mechanistic role of Cu in p-GaN/Al2O3/Au/Cu under unassisted photocatalytic operating conditions using Cu K-edge X-ray absorption spectroscopy and first-principles calculations. Upon exposure to gas-phase CO2 and H2O vapor reaction conditions, the composition of the Cu nanoparticles is identified as a mixture of CuI and CuII oxide, hydroxide, and carbonate compounds without metallic Cu. These composition changes, indicating oxidative conditions, are rationalized by bulk Pourbaix thermodynamics. Under photocatalytic operating conditions with visible light excitation of the plasmonic Au nanoparticles, further oxidation of CuI to CuII is observed, indicating light-driven hole transfer from Au-to-Cu. This observation is supported by the calculated band alignments of the oxidized Cu compositions with plasmonic Au particles, where light-driven hole transfer from Au-to-Cu is found to be thermodynamically favored. These findings demonstrate that under unassisted (unbiased) gas-phase reaction conditions, Cu is found in carbonate-rich oxidized compositions rather than metallic Cu. These species then act as the active cocatalyst and play an oxidative rather than a reductive role in catalysis when coupled with plasmonic Au particles for light absorption, possibly opening an additional channel for water oxidation in this system.

CeO2-CuO composites prepared via supercritical antisolvent precipitation for photocatalytic hydrogen production from lactic acid aqueous solution

The global increase in energy demand requires a continuous search for renewable and clean alternative resources to fossil fuels. Hydrogen is emerging as a promising energy carrier for the future; its production via photocatalysis, driven by sunlight, can directly convert solar energy into a usable or storable energy resource. However, water splitting requires sacrificial agents or electron donors/hole scavengers, such as short-chain organic acids. This research explores the use of lactic acid as a source for photocatalytic hydrogen production, offering valuable alternatives for wastewater management and renewable energy production. This study employed the innovative supercritical antisolvent (SAS) technique to micronize the precursors of both the active phase (CeO2) and co-catalyst (CuO), ensuring rapid and complete solvent removal and size reduction of photocatalyst precursors. The prepared samples were characterized by field emission scanning electron microscopy (FESEM), Fourier transform infrared (FT-IR) spectroscopy, dynamic light scattering (DLS) analysis, Brunauer-Emmett-Teller (BET) analysis and thermogravimetric analysis (TGA). This study has shown that the micronization process resulted in a notable improvement in CeO2 photocatalytic activity, attributed to the reduction of the dimensions of the powders. Hydrogen production was equal to 3989 μmol L−1 for the SAS-produced photocatalyst while using a commercial CeO2 sample resulted in H2 production of 2519 μmol L−1. The enhanced photoactivity of CeO2-CuO composites was found to be related to the presence of CuO. The optimal CuO amount was equal to 0.5 wt%, determining a hydrogen production of 9313 μmol L−1 after 4 h of UV irradiation time. A photocatalytic test carried out with deuterated water (D2O) instead of distilled H2O demonstrated that hydrogen was preferentially produced from water splitting reaction, whereas lactic acid acted as a sacrificial agent being oxidized from positive holes photogenerated in the valence band of CuO.

2D MoB MBene: An Efficient Co-Catalyst for Photocatalytic Hydrogen Production under Visible Light.

Highly active and low-cost co-catalysts have a positive effect on the enhancement of solar H2 production. Here, we employ two-dimensional (2D) MBene as a noble-metal-free co-catalyst to boost semiconductor for photocatalytic H2 production. MoB MBene is a 2D nanoboride, which is directly made from MoAlB by a facile hydrothermal etching and manual scraping off process. The as-synthesized MoB MBene with purity >95 wt % is treated by ultrasonic cell pulverization to obtain ultrathin 2D MoB MBene nanosheets (∼0.61 nm) and integrated with CdS via an electrostatic interaction strategy. The CdS/MoB composites exhibit an ultrahigh photocatalytic H2 production activity of 16,892 μmol g-1 h-1 under visible light, surpassing that of pure CdS by an exciting factor of ≈1135%. Theoretical calculations and various measurements account for the high performance in terms of Gibbs free energy, work functions, and photoelectrochemical properties. This work discovers the huge potential of these promising 2D MBene family materials as high-efficiency and low-cost co-catalysts for photocatalytic H2 production.

Molybdenum oxide/nickel molybdenum oxide heterostructures hybridized active platinum co-catalyst toward superb-efficiency water splitting catalysis

A new catalyst has been developed that utilizes molybdenum oxide (MoO3)/nickel molybdenum oxide (NiMoO4) heterostructured nanorods coupled with Pt ultrafine nanoparticles for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) toward industrial-grade water splitting. This catalyst has been synthesized using a versatile approach and has shown to perform better than noble-metals catalysts, such as Pt/C and RuO2, at industrial-grade current level (≥1000 mA·cm−2). When used simultaneously as a cathode and anode, the proposed material yields 10 mA·cm−2 at a remarkably small cell voltage of 1.55 V and has shown extraordinary durability for over 50 h. Density functional theory (DFT) calculations have proved that the combination of MoO3 and NiMoO4 creates a metallic heterostructure with outstanding charge transfer ability. The DFT calculations have also shown that the excellent chemical coupling effect between the MoO3/NiMoO4 and Pt synergistically optimize the charge transfer capability and Gibbs free energies of intermediate species, leading to remarkably speeding up the reaction kinetics of water electrolysis.

Cocatalyst activity mapping for photocatalytic materials revealed by the pattern-illumination time-resolved phase microscopy.

Photocatalytic water-splitting represents a promising avenue for clean hydrogen production, necessitating an in-depth understanding of the photocatalytic reaction mechanism. The majority of the photocatalytic materials need cocatalysts to enhance the photo-oxidation or reduction reactions. However, the working mechanism, such as collecting charge carriers or reducing the reaction barrier, is not clear because they disperse inhomogeneously on a surface, and it is difficult to follow the local charge carrier behavior. This study employs the pattern-illumination time-resolved phase microscopy (PI-PM) method to unravel the spatial charge carrier behavior in photocatalytic systems, utilizing time-resolved microscopic image (refractive index change) sequences and their clustering analyses. This approach is robust for studying the change in local charge carrier behavior. We studied two major cocatalyst effects on photocatalysts: TiO2 with/without Pt and hematite with/without CoPi. The PI-PM method, supported by charge type clustering and the effects of scavengers, allowed for the analysis of local activity influenced by cocatalysts. This approach revealed that the introduction of cocatalysts alters the local distribution of charge carrier behavior and significantly impacts their decay rates. In TiO2 systems, the presence of Pt cocatalysts led to a local electron site on the micron scale, extending the lifetime to a few tens of microseconds from a few microseconds. Similarly, in hematite films with CoPi, we observed a notable accumulation of holes at cocatalyst sites, emphasizing the role of cocatalysts in enhancing photocatalytic efficiency. The study's findings highlight the complexity of charge carrier dynamics in photocatalytic processes and the significant influence of cocatalysts.

Physical Grinding of Prefabricated Co3O4 and MCM-22 Zeolite for Fischer-Tropsch Synthesis: Impact of Pretreatment Procedure on the Dispersion and Catalytic Performance.

To improve the mess-specific activity of Co supported on zeolite catalysts in Fischer-Tropsch (FT) synthesis, the Co-MCM-22 catalyst was prepared by simply grinding the MCM-22 with nanosized Co3O4 prefabricated by the thermal decomposition of the Co(II)-glycine complex. It is found that this novel strategy is effective for improving the mess-specific activity of Co catalysts in FT synthesis compared to the impregnation method. Moreover, the ion exchange and calcination sequence of MCM-22 has a significant influence on the dispersion, particle size distribution, and reduction degree of Co. The Co-MCM-22 prepared by the physical grinding of prefabricated Co3O4 and H+-type MCM-22 without a further calcination process exhibits a moderate interaction between Co3O4 and MCM-22, which results in the higher reduction degree, higher dispersion, and higher mess-specific activity of Co. Thus, the newly developed method is more controllable and promising for the synthesis of metal-supported catalysts.

A tungsten phosphide cocatalyst enhanced bismuth tungstate photoanode with the robust built-in electric field towards highly efficient photoelectrochemical water splitting

The use of low-cost and effective cocatalyst is a potential strategy to optimize the effectiveness of photoelectrochemical (PEC) water splitting. In this study, tungsten phosphide (WP) is introduced as a remarkably active cocatalyst to enhance the PEC efficiency of a Bi2WO6 photoanode. The onset potential of Bi2WO6/WP demonstrates a negative shift, while the photocurrent density demonstrates a significant 5.5-fold increase compared to that of unmodified Bi2WO6 at 1.23 VRHE (reversible hydrogen electrode). The loading of WP cocatalyst facilitates the rapid transfer of holes, increasing the range of visible light absorption, the water adsorption ability as well as promoting the separation of photogenerated electrons and holes via the built-in electric field between Bi2WO6 and WP. This study proposes a strategy to hinder the recombination of electron-hole pairs by using WP cocatalyst as a hole capture agent, improve the photoelectric conversion efficiency, and enhance the overall photoelectrochemical properties of Bi2WO6 photoanode.

Prussian blue analogues-derived 2D NiCo@C bimetals grown on g-C3N4 as photocatalysts for hydrogen evolution

The development of highly active and stable cocatalysts using earth-abundant transition metals to replace noble metals is important for the application of photocatalytic hydrogen production technology. In this study, two-dimensional (2D) carbon-encapsulated NiCo bimetallic nanosheets (NiCo@C) was designed for the first time as a new co-catalyst to synergistically combine with graphitic carbon nitride (g-C3N4) and promote its hydrogen evolution. The NiCo@C cocatalysts were using an innovative molten salt method by using nickel hexacyanocobaltate Ni3[Co(CN)6]2 (Ni-Co PBA) nanocubes as precursor. The Ni-Co PBA nanocubes undergo dissolution growth and salt templating processes to form bimetallic 2D nanosheets during charring in molten salt media, and combine with 2D g-C3N4 to form NiCo@C/g-C3N4 photocatalyst. The optimized NiCo@C/g-C3N4 photocatalyst significantly improved the H2 evolution activity, and the H2 evolution rate reached 3791.07 μmol·g−1·h−1, which was 5 times higher than that of the particle CoNi/g-C3N4 (636.89 μmol·g−1·h−1). The H2 evolution activity was also comparable to that of the photocatalytic activity of 1.0% Pt/g-C3N4 system, indicating that the earth-abundant NiCo@C can replace noble metal as a cocatalyst to significantly enhance the photocatalytic performance of 2D photocatalysts. The conversion of three-dimensional Ni-Co PBA into carbon-coated 2D metal nanosheets by molten salt-assisted pyrolysis provides a feasible approach to explore the synthesis and design of efficient and robust non-precious metal catalysts.

Nicop Anchored Porous Ti3C2tx Support with 3D Interconnected Structure for Advanced Hydrogen Evolution Reaction Electrocatalysts

MXene have gained much attention as promising electrocatalysts for noble metal-free hydrogen evolutrion reaction (HER) electrocatalysts owing to their high electrical conductivity, hydrophilic surfaces, abundant functional groups, and rational design for hybridization with other materials. In this study, a novel porous monolayered-Ti3C2TX@NiCoP (P-Ti3C2Tx@NiCoP) nanostructure was developed with 3D interconnected structure to significantly improve charge transfer capability and electrocatalytic activity. A strategic approach of modifying pristine Ti3C2Tx monolayers and combining them with other active cocatalysts. Specifically, the H2O2-utilized oxidation and HF etching process formed a highly microporous structure with a maximized surface area of monolayered MXenes as the support. A subsequent solvothermal process followed by phosphidation enabled successful anchoring of highly HER-active NiCoP nanoclusters onto abundantly exposed terminal edges of the P-Ti3C2Tx support. The structural porosity of the P-Ti3C2Tx nanoflakes played an important role in creating additional room for embedding catalytically active species while stably imparting high electrical conductivity to accelerate charge transfer to NiCoP nanoclusters. Moreover, inspired by the pH dependent change of structural arrangement of the Ti3C2Tx, we successfully induced 3D-interconnetecd structure by modulating surface electrostatic forces among Ti3C2Tx monolayers. Of note, the 3D-interconnected structure would shift charge transfer behavior from intermolecular to intramolecular aspects and this would contribute to enhanced charge transfer kinetics. With structural modification of support material and effective hybridization of active species, P-Ti3C2Tx@NiCoP showed highly enhanced HER activity with significantly lower overpoential of 115 and 101 mV at a current density of -10 mA cm-2 in 0.5 M H2SO4 and 1.0 M KOH, respectively, along with showing long-term stability over 60 h. As such, our approach of designing structurally modified-Ti3C2Tx and hybridization with other electrocatalytically active species would function as a solid platform for implementing Ti3C2Tx-based hetero-nanostructures to achieve state-of-the-art performance in next-generation energy conversion applications.

Carbonized eggshell membranes as highly active co-catalyst with Fe3+/persulfate for boosting degradation of carbamazepine by accelerating Fe3+/Fe2+ cycle

The sluggish Fe3+/Fe2+ cycle greatly limits the effectiveness of the Fe3+-induced persulfate (Fe3+/PS) system for degrading refractory organic pollutants. Coupling Fe3+/PS system with a co-catalyst is a promising strategy to solve this issue. Herein, we report a carbonized eggshell membrane (CESM) as a potential co-catalyst to efficiently drive Fe3+/PS oxidation. The promotion effect of the CESM on the Fe3+/Fe2+ cycle resulted in the improvement in the activity of the Fe3+/PS system to degrade carbamazepine (CBZ), with ∼100 % CBZ removal achieved with low doses of Fe3+ (1.0 mg/L) and PS (100 mg/L). Crucially, a pseudo-first-order rate constant of CESM/Fe3+/PS system was 18- and 28-times that of the Fe3+/PS and CESM/PS systems. Experimental and theoretical findings reveal that the phenolic –OH groups and carbon--center persistent free radicals in CESM are electron donors, while the nitrogen sites function as favorable Fe3+-adsorption sites. The electron transfer in CESM/Fe3+/PS system occurred between a CESM and an attached Fe3+, facilitating the generation of Fe2+ and thus contributing to the continuous activation of PS. The quenching and electron paramagnetic resonance results indicate that active oxygen radicals (O2•−,•OH and SO4•−) and Fe(IV) acted together to realize the efficient CBZ degradation. Moreover, this system exhibited good reusability and environmental adaptability in various real water matrices. The co-catalyst effect of CESM is expected to inspire the exploration of utilization of different waste-biomass-derived organic materials as co-catalysts in the Fe3+/PS system for water purification.

Reactive Deposition Versus Strong Electrostatic Adsorption (SEA): A Key to Highly Active Single Atom Co-Catalysts in Photocatalytic H2 Generation.

In recent years, the use of single atoms (SAs) has become of a rapidly increasing significance in photocatalytic H2 generation; here SAnoble metals (mainly Pt SAs) can act as highly effective co-catalysts. The classic strategy to decorate oxide semiconductor surfaces with maximally dispersed SAs relies on "strong electrostatic adsorption" (SEA) of suitable noble metal complexes. In the case of TiO2 - the classic benchmark photocatalyst - SEA calls for adsorption of cationic Pt complexes such as [(NH3 )4 Pt]2+ which then are thermally reacted to surface-bound SAs. While SEA is widely used in literature, in the present work it is shown by a direct comparison that reactive attachment based on the reductive anchoring of SAs, e.g., from hexachloroplatinic(IV) acid (H2 PtCl6 )leads directly to SAs in a configuration with a significantly higher specific activity than SAs deposited with SEA - and this at a significantly lower Pt loading and without any thermal post-deposition treatments. Overall, the work demonstrates that the reactive deposition strategy is superior to the classic SEA concept as it provides a direct electronically well-connected SA-anchoring and thus leads to highly active single-atom sites in photocatalysis.

Optimizing intrinsic cocatalyst activity and light absorption efficiency for efficient hydrogen evolution of 1D/2D ReS2-CdS photocatalysts via control of ReS2 nanosheet layer growth

The visible-light-driven hydrogen evolution is extremely important, but the poor charge transfer capability, a sluggish evolution rate of hydrogen, and severe photo-corrosion make photocatalytic hydrogen evolution impractical. In this study, we present 1D/2D ReS2-CdS hybrid nanorods for photocatalytic hydrogen evolution, comprised of a ReS2 nanosheet layer grown on CdS nanorods. We found that precise control of the contents of the ReS2 nanosheet layer allows for manipulating the electronic structure of Re in the ReS2-CdS hybrid nanorods. The ReS2-CdS hybrid nanorods with optimal ReS2 nanosheet layer content dramatically improve photocatalytic hydrogen evolution activity. Notably, photocatalytic hydrogen evolution activity (64.93 mmol g−1 h−1) of ReS2-CdS hybrid nanorods with ReS2 nanosheet layers (Re/Cd atomic ratio of 0.051) is approximately 136 times higher than that of pure CdS nanorods under visible light irradiation. Furthermore, intimated coupling of the ReS2 nanosheet layer with CdS nanorods reduced the surface trap-site of the CdS nanorods, resulting in enhanced photocatalytic stability. The detailed optical and electrical investigations demonstrate that the optimal ReS2 nanosheet layer contents in the ReS2-CdS hybrid nanorods can provide improved charge transfer capability, catalytic activity, and light absorption efficiency. This study sheds light on the development of photocatalysts for highly efficient photocatalytic hydrogen evolution.

A MOF-derived Bimetallic Co-catalyst for Promoting Visible-light Photocatalytic Hydrogen Evolution on NH2 -MIL-125.

In order to construct noble metal-free co-catalysts to facilitate the transport and separation of photocatalyst carriers, herein, a MOF-based derived bimetallic NiCu0.2 co-catalyst was loaded on NH2 -MIL-125(Ti). The obtained NiCu0.2 /NH2 -MIL-125 exhibited a photocatalytic activity of 161.4 μmol g-1 h-1 for hydrogen evolution, 12.6 times higher than that of the Ni/NH2 -MIL-125 and even slightly better than Pt/NH2 -MIL-125. The work expands the development pathway of cost-effective and highly active bimetallic co-catalysts for photocatalytic H2 evolution.

Engineering hydrogenated TiO2 nanosheets by rational deposition of Ni clusters and Pt single atoms onto exposing facets for high-performance solar fuel production

The rational deposition of active atomic cocatalysts onto the exposing facets of photocatalysts is challenging. Herein, following the theoretical guidance, Pt single atoms (SAs) and Ni nanoclusters (NCs) have been introduced onto the (001) facet and a small amount of Ni clusters have been introduced are deposited on (101) facet of hydrogenated TiO2 nanosheets by a room temperature H2/Ar plasma method. The resulted H-TiO2@Pt SAs-Ni NCs exhibits high-performance solar hydrogen evolution with a rate of 71 mmol/g/h. Photoelectrochemical tests and theoretical simulation show that the introducing Ni-Pt brings about new external energy levels, elevates the valence band and suppresses the recombination of photo-generated electrons and holes. The computational results confirm that the H-O bond of the adsorbed H2O molecule was significantly activated on the Pt SAs-TiO2, and Ni NCs-TiO2. The co-promotion effect of Pt SAs and Ni NCs facilitates the enhanced performance. This work provides new opportunity for the design of advanced crystal facet-induced engineering nano-catalysts.

Hollow core-shell LDH@N-HCS/CN S-scheme photocatalyst with the enhanced visible-light activity

It is a great challenge to effectively increase the charge separation and active sites of earth-abundant graphitic carbon nitride (CN) semiconductors to improve the photocatalytic performance. Looking for a highly active cocatalyst has attracted attention because of their potential to resolve the issues of low charge separation and low specific surface area of CN. A core-shell cocatalyst composed of nitrogen doped hollow carbon spheres (N-HCS) as the core and LDH nanoplates as the photoactive shell has been designed to increase the pristine CN active sites and charge separation. N-HCS acted as the support for LDH nanoplates to prevent particle agglomeration and served as the fast electron transfer channels to enhance the photoinduced charge separation efficiency. The ternary nanocomposites exhibited superior activity for nonyl phenol and Acid Blue 92 degradation compared to the unmodified CN under the visible light. The optimized deposition of LDH@N-HCS (15 wt%) on the CN surface resulted in 7-fold higher activity than without the cocatalyst. The improved photocatalytic activity of the ternary composite compared to CN could be attributed to two factors: efficient electron-hole pair separation due to LDH nanoplates and CN interface, and the presence of the N-HCS as an electron collector. The porous hollow structure of the cocatalyst exposes the numerous surface-active sites that favor visible light photocatalytic performance and supplies multiple reflection of photons into the cavity, increasing the usage ratio of light. This work will supply a novel strategy to rationally fabricate a noble metal-free binary cocatalyst for efficient visible light activity.

Single-Atom Phosphorus Defects Decorated CoP Cocatalyst Boosts Photocatalytic Hydrogen Generation Performance of Cd0.5 Zn0.5 S by Directed Separating the Photogenerated Carriers.

Design and preparation of an efficient and nonprecious cocatalysts, with structural features and functionality necessary for improving photocatalytic performance of semiconductors, remain a formidable challenge until now. Herein, for the first time, a novel CoP cocatalyst with single-atom phosphorus vacancies defects (CoP-Vp ) is synthesized and coupled with Cd0.5 Zn0.5 S to build CoP-Vp @Cd0.5 Zn0.5 S (CoP-Vp @CZS) heterojunctions photocatalysts via a liquid phase corrosion method following by an in suit growth process. The nanohybrids deliver an attractive photocatalytic hydrogen production activity of 2.05mmol h-1 30 mg-1 under visible-light irradiation, which is 14.66 times higher than that of the pristine ZCS samples. As expected, CoP-Vp further enhances the charge-separation efficiency of ZCS, in addition to the improvement of the electron transfer efficiency, which is confirmed by the ultrafast spectroscopies. Mechanism studies based on density functional theory calculations verify that Co atoms adjacent with single-atom Vp play the key role in translation, rotation, and transformation of electrons for H2 O reduction. This scalable strategy focusing defect engineering provides a new insight into designing the highly active cocatalysts to boost the photocatalytic application.

Tungsten disulfide (WS2) is a highly active co-catalyst in Fe(III)/H2O2 Fenton-like reactions for efficient acetaminophen degradation

The most important factor that restricts the decomposition of H2O2 in the Fe3+/H2O2 reaction is the slow cycling efficiency of reducing Fe3+ to Fe2+. In this study, the addition of tungsten disulfide (WS2) as a co-catalyst achieved a rapid cycling of the reaction rate-limiting step and a significant enhancement of H2O2 decomposition, which resulted in the effective degradation of acetaminophen (APAP). Results show that 99.6% of APAP (5 mg L−1) could be degraded by H2O2/Fe3+/WS2 system within 2.5 min. The conversion of Fe3+ to Fe2+ occurred mainly on the surface of WS2 due to the redox reaction of the exposed W4+ active sites with Fe3+ after the unsaturated S atoms were bound to protons. Electron paramagnetic resonance (EPR) and radical quenching experiments evaluated the contribution of hydroxyl radical (•OH) and superoxide radical (O2•−) in the degradation of pollutants. WS2 showed good recoverability after four cycles of the reaction. This study provides a new perspective to improve the efficiency of Fe3+/H2O2 and provides a reference for the involvement of transition metal sulfides in advanced oxidation processes (AOPs).

CeO2-based oxygen storage capacity materials in environmental and energy catalysis for carbon neutrality: extended application and key catalytic properties

ABSTRACT Reducing carbon dioxide emissions is one of the largest energy and environmental challenges currently faced globally. To achieve carbon neutrality, the development of new technologies and simultaneous improvement of conventional technologies are required. Catalysis, which determines the success or failure and efficiency of the process, is at the center of addressing these problems. Innovative advancements in catalysis have been accomplished through the extensive research on catalytic materials. Oxygen storage materials with oxygen storage capacity (OSC) have been widely applied in supports and active cocatalysts for energy and environmental catalytic applications. This review provides knowledge on the extended applications (reforming, water-gas shift reaction, and partial oxidation of methane (POM) for high-value-added chemicals, including hydrogen production, deoxygenation of fatty acids for second-generation biofuel production, selective catalytic reduction of NO x with NH3, hydrocarbon (HCs) oxidation for emission control, CO oxidation for vehicle exhaust control and purification of gaseous product fuel, and soot oxidation for the removal of motor-type pollutants) of these materials, which are mainly used as three-way catalysts (TWC) in automotive catalysis, to the carbon-neutral field. In particular, this study focuses on the physico-chemical properties that are closely synergistic with OSC, such as reducibility, dispersion, surface acid/base properties, and physical properties, such as surface structure or morphology.