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Bismuth vanadate (BVO) having suitable band edges is one of the effective photocatalysts for water oxidation, which is the rate-determining step in the water splitting process. Incorporating cocatalysts can reduce activation energy, create hole sinks, and improve photocatalytic ability of BVO. In this work, the visible light active nickel tellurium oxide (NTO) is used as the cocatalyst on the BVO photoanode to improve photocatalytic properties. Different NTO amounts are deposited on the BVO to balance optical and electrical contributions. Higher visible light absorbance and effective charge cascades are developed in the NTO and BVO composite (NTO/BVO). The highest photocurrent density of 6.05 mA/cm2 at 1.23 V versus reversible hydrogen electrode (VRHE) and the largest applied bias photon-to-current efficiency (ABPE) of 2.13% are achieved for NTO/BVO, while BVO shows a photocurrent density of 4.19 mA/cm2 at 1.23 VRHE and ABPE of 1.54%. Excellent long-term stability under light illumination is obtained for NTO/BVO with photocurrent retention of 91.31% after 10,000 s. The photoelectrochemical catalytic mechanism of NTO/BVO is also proposed based on measured band structures and possible interactions between NTO and BVO. This work has depicted a novel cocatalytic BVO system with a new photocharging material and successfully achieves high photocurrent densities for catalyzing water oxidation.
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Efficient hydrogen (H2) production through photocatalytic water splitting was achieved by using an amino-functionalized azolate/cobalt-based metal-organic framework (MOF). While previous reports highlighted the amino group's role only as a substituent group for enabling light absorption of MOFs in the visible region, our present study revealed its dual role. The amino substituent not only acts as an electron donor to increase the electron availability at the active Co sites but also provides hydrogen-hopping sites within the pore channel, facilitating proton (H+) diffusion along the framework. This dual functionality significantly boosts the performance of this Co-MOF as a hydrogen evolution cocatalyst. When combined with fluorescein and triethylamine as the photosensitizer and sacrificial agent, respectively, the Co-MOF achieved a remarkable H2 production rate of 27 mmol g-1 over 4 h. Notably, this performance surpasses those of benchmark platinum (Pt) and titanium dioxide (TiO2) cocatalysts.
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The photocatalytic hydrogen production performance of semiconductor materials can be improved by co-catalyst modification. In most of the studies, the size of the co-catalyst is relatively small compared to the primary catalyst. However, in this study, we employed a novel strategy by synthesizing a relatively large-sized Cu2MoS4 as the co-catalyst and in situ loading smaller-sized Zn0.5Cd0.5S onto Cu2MoS4, verifying that Cu2MoS4 enhances the photocatalytic hydrogen production efficiency of Zn0.5Cd0.5S. It can be observed by scanning electron microscopy (SEM) that the lateral size of 2D Cu2MoS4 is at least 50 times larger than the Zn0.5Cd0.5S nanoparticle particle size. In addition, Density Functional Theory (DFT) calculations have demonstrated that the active site for hydrogen production in the composite is located in Cu2MoS4. The large-sized of Cu2MoS4 not only provides more active sites but also broadens the electron transport channel, which is conducive to promoting the transfer of photogenerated electrons from Zn0.5Cd0.5S. This work enriches the study of large-sized materials as co-catalyst and provides a strategy for the construction of composite catalysts.
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Suitable H2O and H adsorption on the surface of transition metal chalcogenide cocatalyst is highly required to achieve their excellent alkaline H2-evolution rate. However, the weak adsorption of H2O and H atoms on NiTe surface greatly hinders its alkaline H2-evolution efficiency. Herein, an electron-deficient modulation strategy is proposed to synchronously improve the adsorption of H2O and H atoms on NiTe surface, which can greatly improve the alkaline photocatalytic H2 evolution of TiO2. In this case, highly electronegative oxygen atoms are introduced into the NiTe cocatalysts to induce the formation of electron-deficient Niδ+ and Teδ+ sites in the ultra-small-sized NiO1-xTex nanodots (0.5-2 nm), which can be uniformly loaded onto the TiO2 surface to prepare the NiO1-xTex/TiO2 photocatalysts by a facile complexation-photodeposition strategy. The resulting NiO1-xTex/TiO2 (0.6:0.4) photocatalyst exhibits the optimal activity (2143.36 µmol g-1 h-1), surpassing the activity levels of TiO2 and NiTe/TiO2 samples by 42.3 and 1.8 times, respectively. The experimental and theoretical investigations have revealed that the presence of highly electronegative O atoms in the NiO1-xTex cocatalyst can redistribute the charges of Ni and Te atoms for the formation of electron-deficient Niδ+ and Teδ+ active sites, thereby synchronously enhancing the adsorption of H2O on Niδ+ sites and H on Teδ+ sites and promoting alkaline photocatalytic H2 evolution. The current research about the synchronous optimization of the H2O and H adsorption offers a significant approach to design high-performance H2-evolution materials.
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The local charge distribution of photocatalyst is crucial to the catalytic activity due to its influence on the charge separation process. Herein, we report two one-dimensional Ni-based metal-organic assemblies for efficient photocatalytic hydrogen evolution without using noble-metal cocatalysts. By adjusting the aromatic ring in the center of the tricarboxylic ligand, the photocatalytic hydrogen evolution activity was increased from 1715 to 2652 µmol h-1 g-1. The detailed mechanism study shows that the introduced nitrogen atoms in the ligands of the metal-organic coordination assembly could modulate the local charge distribution, and yielding a significant enhancement of the molecular dipole moment which engenders a propulsive force for the effective separation and transport of photoinduced charge carriers. This work provides insights into the local charge distribution via ligand modulation for enhancing the activity of photocatalysts.
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CdS quantum dots (CdS QDs) are regarded as a promising photocatalyst due to their remarkable response to visible light and suitable placement of conduction bands and valence bands. However, the problem of photocorrosion severely restricts their application. Herein, the CdS QDs-Co9S8 hollow nanotube composite photocatalyst has been successfully prepared by loading Co9S8 nanotubes onto CdS QDs through an electrostatic self-assembly method. The experimental results show that the introduction of Co9S8 cocatalyst can form a stable structure with CdS QDs, and can effectively avoid the photocorrosion of CdS QDs. Compared with blank CdS QDs, the CdS QDs-Co9S8 composite exhibits obviously better photocatalytic hydrogen evolution performance. In particular, CdS QDs loaded with 30% Co9S8 (CdS QDs-30%Co9S8) demonstrate the best photocatalytic performance, and the H2 production rate reaches 9642.7 µmol·g-1·h-1, which is 60.3 times that of the blank CdS QDs. A series of characterizations confirm that the growth of CdS QDs on Co9S8 nanotubes effectively facilitates the separation and migration of photogenerated carriers, thereby improving the photocatalytic hydrogen production properties of the composite. We expect that this work will facilitate the rational design of CdS-based photocatalysts, thereby enabling the development of more low-cost, high-efficiency and high-stability composites for photocatalysis.
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Mo2C MXene (Mo2CTx) is one of the most promising noble-metal-free cocatalysts for photocatalytic H2 production because of its excellent electron transport capacity and abundant Mo sites. However, Mo2CTx typically exhibits a strong MoâHads bond, resulting in that the produced H2 difficultly desorbs from the Mo surface for the limited activity. To effectively weaken the MoâHads bond, in this paper, a regulation strategy of electron donor Au releasing electrons to the d-orbitals of Mo sites in Mo2CTx is proposed. Herein, the Mo2CTx-Au/CdS photocatalysts are prepared through a two-step process, including the initial loading of Au nanoparticles on the Mo2CTx surface and the subsequent in situ growth of CdS onto the Mo2CTx-Au surface. Photocatalytic measurements indicate that the maximal H2-production rate of Mo2CTx-Au/CdS reaches up to 2799.44 µmol g-1 h-1, which is 30.99 and 3.60 times higher than that of CdS and Mo2CTx/CdS, respectively. Experimental and theoretical data corroborate that metallic Au can transfer free electrons to Mo2CTx to generate electron-enriched Moδ- sites, thus causing the increased antibonding-orbital occupancy state and the weakened MoâHads bond for the boosted H2-production efficiency. This research provides a promising approach for designing Mo2CTx-based cocatalysts by regulating the antibonding-orbital occupancy of Mo sites for improved photocatalytic performance.
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This study explores the optimal morphology of photochemical hydrogen evolution catalysts in a one-dimensional system. Systematic engineering of metal tips on precisely defined CdSe@CdS dot-in-rods is conducted to exert control over morphology, composition, and both factors. The outcome yields an optimized configuration, a Au-Pt core-shell structure with a rough Pt surface (Au@r-Pt), which exhibits a remarkable fivefold increase in quantum efficiency, reaching 86% at 455 nm and superior hydrogen evolution rates under visible and AM1.5G irradiation conditions with prolonged stability. Kinetic investigations using photoelectrochemical and time-resolved measurements demonstrate a greater extent and extended lifetime of the charge-separated state on the tips as well as rapid water reduction kinetics on high-energy surfaces. This approach sheds light on the critical role of cocatalysts in hybrid photocatalytic systems for achieving high performance.
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The conversion of CO2 into liquid fuels, using only sunlight and water, offers a promising path to carbon neutrality. An outstanding challenge is to achieve high efficiency and product selectivity. Here, we introduce a wireless photocatalytic architecture for conversion of CO2 and water into methanol and oxygen. The catalytic material consists of semiconducting nanowires decorated with core-shell nanoparticles, with a copper-rhodium core and a chromium oxide shell. The Rh/CrOOH interface provides a unidirectional channel for proton reduction, enabling hydrogen spillover at the core-shell interface. The vectorial transfer of protons, electrons, and hydrogen atoms allows for switching the mechanism of CO2 reduction from a proton-coupled electron transfer pathway in aqueous solution to hydrogenation of CO2 with a solar-to-methanol efficiency of 0.22%. The reported findings demonstrate a highly efficient, stable, and scalable wireless system for synthesis of methanol from CO2 that could provide a viable path toward carbon neutrality and environmental sustainability.
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Metal halide perovskites (MHPs) have emerged as attractive candidates for producing green hydrogen via photocatalytic pathway. However, the presence of abundant defects and absence of efficient hydrogen evolution reaction (HER) active sites on MHPs seriously limit the solar-to-chemical (STC) conversion efficiency. Herein, to address this issue, we present a bi-functionalization strategy through decorating MHPs with a molecular molybdenum-sulfur-containing co-catalyst precursor. By virtue of the strong chemical interaction between lead and sulfur and the good dispersion of the molecular co-catalyst precursor in the deposition solution, a uniform and intimate decoration of the MHPs surface with lead sulfide (PbS) and amorphous molybdenum sulfide (MoSx) co-catalysts is obtained simultaneously. We show that the PbS co-catalyst can effectively passivate the Pb-related defects on the MHPs surface, thus retarding the charge recombination and promoting the charge transfer efficiency significantly. The amorphous MoSx co-catalyst further promotes the extraction of photogenerated electrons from MHPs and facilitates the HER catalysis. Consequently, drastically enhanced photocatalytic HER activities are obtained on representative MHPs through the synergistic functionalization of PbS and MoSx co-catalysts. A solar-to-chemical (STC) conversion efficiency of ca. 4.63% is achieved on the bi-functionalized FAPbBr3-xIx, which is among the highest values reported for MHPs.
RESUMEN
Element doping has been demonstrated as a useful strategy to regulate the band gap and electronic structure of photocatalyst for improving photocatalytic activity. Herein, ZnIn2S4 (ZIS) nanosheets were doped with alkali metal ions (Li+, Na+ or K+) by a simple solution method. Experimental characterizations reveal that alkali metal ions doping reduce the band gap, raise the conduction band position, and improve surface hydrophilicity of ZIS. In addition, theoretical calculations show that Na doping increases the electron density at valence band maximum and surrounding S atom, which is conducive to produce more electrons and effective utilization of electrons, respectively. Benefited from above factors, Na-doped ZIS (Na-ZIS) shows the highest photocatalytic hydrogen evolution performance. Furthermore, CoSe2 cocatalyst is loaded on the surface of Na-ZIS (CS/Na-ZIS), which further improve the charge separation and prolong the lifetime of charges. As a result, the optimized CS/Na-ZIS shows a H2 evolution rate of 4525 µmol·g-1·h-1 with an apparent quantum efficiency of 27.5 % at 420 nm, which are much higher than that of pure ZIS. This study provides an in-depth understanding of the synergistic effect of Na doping and CoSe2 cocatalyst in ameliorating photocatalytic activity.
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Despite the excellent photocatalytic activity under visible light, graphitic carbon nitride (g-C3N4) exhibits a high overpotential for hydrogen evolution. To address this issue, cocatalysts have been utilized to modify g-C3N4. However, the use of high-performance cocatalysts typically involves noble metals such as platinum and palladium, which are cost-prohibitive for practical applications. Therefore, the development of efficient and cost-effective cocatalysts is crucial for advancing photocatalysis. In this study, we synthesized a new Ni-based cocatalyst, nickel thiocarbonate (NiCS3), to enhance the photocatalytic hydrogen evolution reaction (HER) on g-C3N4. The NiCS3/g-C3N4 composite demonstrated a significantly increased hydrogen evolution rate of 951 µmol·h-1·g-1 under visible light, representing more than a 105-fold improvement compared to pure g-C3N4. Theoretical calculations suggested that the enhanced performance in photocatalytic hydrogen production can be attributed to the generation of a built-in electric field within the composite, facilitating efficient charge carrier separation and migration. Additionally, the C site in NiCS3 provides a favorable Gibbs free energy of adsorbed H* (ΔGH∗). This work underscores the potential of NiCS3 as a viable alternative to precious metals in photocatalytic hydrogen production using g-C3N4.
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The sustainable generation of ammonia by photocatalytic nitrogen fixation under mild conditions is fascinating compared to conventional industrial processes. Nevertheless, owing to the low charge transfer efficiency, the insufficient light absorption capacity and limited active sites of the photocatalyst cause the difficult adsorption and activation of N2 molecules, thereby resulting in a low photocatalytic conversion efficiency. Herein, a novel bimetallic CoMoB nanosheets (CoMoB) co-catalyst modified carbon nitride with dual moiety defects (CN-TH3/3) Schottky junction photocatalyst is designed for photocatalytic nitrogen reduction reaction (NRR). The photocatalytic nitrogen reduction rate of the optimized CoMoB/CN-TH3/3 photocatalyst is 4.81 mM·g-1·h-1, which is 6.2 and 2.2 times higher than carbon nitride (CN) (0.78 mM·g-1·h-1) and CN-TH3/3 (2.21 mM·g-1·h-1), respectively. The excellent photocatalytic NRR performance is ascribed not only to the introduction of dual moiety defects (cyano and cyanamide groups) that extends the visible light absorption range and promotes exciton polarization dissociation, but also to the formation of interfacial electric field between CoMoB and CN-TH3/3, which effectively facilitates the interfacial charge transfer. Thus, the synergistic interaction between CN-TH3/3 and CoMoB further increases the electron numble of CoMoB active sites, which effectively strengthens the adsorption and activation of N2 and weakens the NN triple bond, thereby enhancing the photocatalytic NRR activity. This work highlights the introduced dual moiety defects and bimetallic CoMoB co-catalyst to synergistically enhance the photocatalytic nitrogen reduction performance.
RESUMEN
Catalysts composed of nanocluster and single-atom (SA) were extensively used to enhance electrocatalytic water splitting performance, whereas study of their photocatalytic hydrogen (H2) evolution activity was limited. Herein, carbon nitride (CN) decorated by ruthenium (Ru) cocatalysts existed as SA + cluster, cluster + nanoparticles (NPs), and NPs were prepared by impregnation and calcination processes. The correlation between existential form, content of Ru cocatalyst and H2 evolution rate were carefully discussed. It was found that Ru NPs were favor for water molecule adsorption, whereas Ru SAs and clusters facilitated H2 desorption. Theoretical calculations revealed that Ru clusters + NPs cocatalyst were beneficial for H* intermediate formation. Water splitting tests found that 1.07 wt% Ru NPs + cluster modified CN showed the highest H2 evolution rate of 13.64 mmol h-1 g-1, which was 266.4 and 1.5 times higher than those of CN and Ru NPs (2.33 wt%) decorated CN, respectively. This work deeply reveals the influences of existential form of Ru cocatalysts on photocatalytic water splitting of CN, and provides thought in designing new cocatalysts to largely enhance H2 evolution.
RESUMEN
Improving the separation efficiency of carriers is an important part of enhancing photocatalytic activity. Herein, we successfully decorated metallic 1T phase tungsten disulfide (1T-WS2) on the surface of zinc indium sulfide (ZnIn2S4) and investigated the synergistic effect of 1T-WS2 on ZnIn2S4. The characterization results show that 1T-WS2 improves the light absorption capacity and utilization efficiency, increases the catalytic active site, improves the photogenerated charge separation efficiency, and optimizes the reduction potential of ZnIn2S4. Theoretical calculations show that compared with ZnIn2S4, 1T-WS2/ZnIn2S4 has a smaller adsorption Gibbs free energy of the intermediate state H*, which is conducive to the catalytic reaction. Under simulated solar irradiation, the hydrogen (H2) production rate of 1T-WS2/ZnIn2S4 with a loading of 12 wt% reaches 30.90 mmol h-1 g-1, which is 3.38 times higher than that of single ZnIn2S4 (9.13 mmol h-1 g-1). In addition, the apparent quantum efficiency of 1T-WS2/ZnIn2S4 with a loading of 12 wt% reaches 21.14 % under monochromatic light at a wavelength of λ = 370 nm. This work analyzes the light absorption and carrier separation to the catalytic site, and elucidates the mechanism for the enhancement of the photocatalytic hydrogen production performance.
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Metallocene catalysts have attracted much attention from academia and industry for their excellent catalytic activity in the field of olefin polymerization. Cocatalysts play a key role in metallocene catalytic systems, which can not only affect the overall catalytic activity, but also have an obvious influence on the structure and properties of the polymer. Although methylaluminoxane (MAO) is currently the most widely used cocatalyst, its price increases the production cost of polyolefin materials. Ammonium tetrakis(pentafluorophenyl)borate has shown excellent performance in polymerization, being one of the best substitutes for the traditional cocatalyst MAO. Compared with the main catalyst, whose composition and structure are relatively complex, the research on cocatalyst is very limited. This review mainly introduces the research history, preparation methods, and application progress in polymerization of ammonium tetrakis(pentafluorophenyl)borate, deepening our understanding of the role of cocatalyst in polymerization, with the hope of inspiring brand-new thinking on improving and enhancing the overall performance of catalyst systems.
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Layered double hydroxides (LDHs), especially those containing nickel (Ni), are increasingly recognized for their potential in photo(-/)electrocatalytic water oxidation due to the abundant availability of Ni, their corrosion resistance, and their minimal toxicity. This review provides a comprehensive examination of Ni-based LDHs in electrocatalytic (EC), photocatalytic (PC), and photoelectrocatalytic (PEC) water oxidation processes. The review delves into the operational principles, highlighting similarities and distinctions as well as the benefits and limitations associated with each method of water oxidation. It includes a detailed discussion on the synthesis of monolayer, ultrathin, and bulk Ni-based LDHs, focusing on the merits and drawbacks inherent to each synthesis approach. Regarding the EC oxygen evolution reaction (OER), strategies to improve catalytic performance and insights into the structural evolution of Ni-based LDHs during the electrocatalytic process are summarized. Furthermore, the review extensively covers the advancements in Ni-based LDHs for PEC OER, including an analysis of semiconductors paired with Ni-based LDHs to form photoanodes, with a focus on their enhanced activity, stability, and underlying mechanisms facilitated by LDHs. The review concludes by addressing the challenges and prospects in the development of innovative Ni-based LDH catalysts for practical applications. The comprehensive insights provided in this paper will not only stimulate further research but also engage the scientific community, thus driving the field of photo(-/)electrocatalytic water oxidation forward.
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In the quest for sustainable energy solutions, the optimization of the photoelectrochemical (PEC) performance of hematite photoanodes through cocatalysts represents a promising avenue. This study introduces a novel machine learning approach, leveraging subtraction descriptors, to isolate and quantify the specific effects of cobalt phosphate (Co-Pi) as a cocatalyst on hematite's PEC performance. By integrating data from various analytical techniques, including photoelectrochemical impedance spectroscopy and ultraviolet-visible spectroscopy, with advanced machine learning models, we successfully predicted the PEC performance enhancement attributed to Co-Pi. The Gaussian process regression (GPR) model emerged as the most effective, revealing the critical influence of the interfacial resistance, bulk resistance, and interfacial capacitance on the PEC performance. These findings underscore the potential of cocatalysts in improving charge separation and extending charge carrier lifetimes, thereby boosting the efficiency of photocatalytic reactions. This study not only advances our understanding of the cocatalyst effect in photocatalytic systems but also demonstrates the power of machine learning in modifying complex materials and guiding the development of optimized photocatalytic materials. The implications of this research extend beyond hematite photoanodes, offering a generalizable framework for enhancing the photoelectrochemical properties of a wide range of material modifications such as cocatalyst deposition, doping, and passivation.
RESUMEN
The capacitance of a co-catalyst can be likened to a "double-edged sword". Α co-catalysts with high capacitance can store photoexcited electrons, thereby facilitating charge separation within the host catalyst. However, this property simultaneously restricts electron release. Both effects are enhanced with an increasing capacitance value, implying that excessively high capacitance can significantly hinder the photocatalytic hydrogen (H2) production reaction. Herein, we have designed a metal-organic framework (MOF) -derived carbon-coated nickel phosphide (C-Ni5P4) as the co-catalyst of cadmium sulfide (CdS). When C-Ni5P4 and CdS are closely interconnected, electrons spontaneously migrate from CdS to C-Ni5P4 under irradiation due to the higher work function (WF) of C-Ni5P4 compared to CdS. Most importantly, although the WF of C-Ni5P4 is 0.1 eV lower than that of Ni5P4, its specific capacitance (1.2 mF/cm2) is also lower than that of Ni5P4 (1.3 mF/cm2). This difference dramatically promotes electron release. Thereby exerting a strong positive effect on capacitance catalysis. Therefore, 7% C-Ni5P4/CdS exhibits exceptional cyclic stability and has a remarkably high activity level of 12283 µmol/h/g and 3.8 times as many as 3.0 %Ni5P4/CdS. This study provides a theoretical basis for the advancement of photocatalysts with high efficiency in H2 production and is expected to be applied in other fields of photocatalysis.
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Due to the complex series of elementary steps involved, achieving deep photoreduction of CO2 to multielectron products such as CH4 remains a challenging task. Therefore, it is crucial to strategically design catalysts that facilitate the controlled formation of the crucial intermediates and provide precise control over the reaction pathway. Herein, we present a pioneering approach by employing polyhydroxy fullerene (PHF) molecules to modify the surface of Ni(OH)2, creating stable and effective synergistic sites to enhance the formation of CH4 from CO2 under light irradiation. As a result, the optimized PHF-modified Ni(OH)2 cocatalyst achieves a CH4 production rate of 455 µmol g-1 h-1, with an electron-based selectivity of approximately 60%. The combination of in situ characterizations and theoretical calculations reveals that the hydroxyl species on the surface of PHF can participate in stabilizing crucial intermediates and facilitating water activation, thereby altering the reaction pathway to form CH4 instead of CO. This study provides a novel approach to regulating the selectivity of photocatalytic CO2 reduction by exploring molecular surface modification through interfacing with functionalized carbon clusters.