Engineering of Ultra-Thin Layer of MIL-125(Ti) Nanosheet\Zn-Tetracarboxy-Phthalocyanine S-Scheme Heterojunction as Photocatalytic CO2 Reduction Catalyst.

Metal-organic frameworks (MOFs) with ultrathin 2D structure have attracted remarkable attention in photocatalytic application owing to the accessibility of abundant active sites on the surface. But high charge recombination results in poor photocatalytic activity. Herein, the synthesis of ultrathin MIL-125(Ti) nanosheets is reported with a thickness of 1.3 nm through a simple chemical reaction route of precursor solution aging and subsequent solvothermal process for photocatalytic CO2 production. The maximal CO evolution rate achieves 200.8 µmol g-1 h-1, which is prominently higher than that (78.6 µmol g-1 h-1) of the bulk MIL-125(Ti) counterpart. Furthermore, the structurally stable Zn (II) tetracarboxy phthalocyanine (ZnTcPc) molecules assembly on ultrathin MIL-125(Ti) nanosheet (NS) to form MIL-125(Ti) NS\ZnTcPc S-scheme heterojunction through the strong interaction between the Ti3+ in MIL-125(Ti) and the COOH in ZnTcPc. The introduction of ZnTcPc greatly extends light absorption range and increases charge separation rate. The experimental and density functional theory calculation results validate that the MIL-125(Ti) NS\ZnTcPc S-scheme heterojunction can favor CO2 adsorption and effectively depress the formation energy of the intermediates, achieving a high CO evolution rate of 450.8 µmol g-1 h-1. This work provides a strategy of engineering 2D MOF-based heterostructure systems for photocatalytic application.

Hierarchical Co0.85 Se-CdSe/MoSe2 /CdSe Sandwich-Like Heterostructured Cages for Efficient Photocatalytic CO2 Reduction.

Fabricating efficient photocatalysts with rapid charge carrier separation and high visible light harvesting is an advisable strategy to improve CO2 reduction performance. Herein, hierarchical Co0.85 Se-CdSe/MoSe2 /CdSe cages with sandwich-like heterostructure are prepared to act as efficient photocatalysts for CO2 reduction. In this study, the structure and composition of the final products can be regulated through the cation-exchange reaction in the presence of ascorbic acid. In the Co0.85 Se-CdSe/MoSe2 /CdSe cages, MoSe2 nanosheets function as a bridge to integrate Co0.85 Se-CdSe and CdSe on both sides of the MoSe2 nanosheet shell into a sandwich-like heterostructured catalyst system, which possesses multiple positive merits for photocatalysis, including accelerated transport and separation of photogenerated carriers, improved visible light utilization, and increased catalytic active sites. Thus, the optimized Co0.85 Se-CdSe/MoSe2 /CdSe cages exhibit remarkable visible-light photocatalytic performance and outstanding stability for CO2 reduction with a high CO average yield of 15.04 µmol g-1 h-1 and 90.14% selectivity, which are much higher than those of other control samples including single-component catalysts and binary hybrid catalysts. This study provides a promising way for the design and fabrication of high-efficiency photocatalysts.

Molecule Self-Assembly Synthesis of Porous Few-Layer Carbon Nitride for Highly Efficient Photoredox Catalysis.

Polymeric carbon nitride (C3N4) has emerged as the most promising candidate for metal-free photocatalysts but is plagued by low activity due to the poor quantum efficiency and low specific surface area. Exfoliation of bulk crystals into ultrathin nanosheets has proven to be an effective and widely used strategy for enabling high photocatalytic performances; however, this process is complicated, time-consuming, and costly. Here, we report a simple bottom-up method to synthesize porous few-layer C3N4, which involves molecule self-assembly into layered precursors, alcohol molecules intercalation, and subsequent thermal-induced exfoliation and polycondensation. The as-prepared few-layer C3N4 expose more active sites and greatly enhance the separation of charge carriers, thus exhibiting a 26-fold higher hydrogen evolution activity than bulk counterpart. Furthermore, we find that both the high activity and selectivity for the oxidative coupling of amines to imines can be obtained under visible light that surpass those of other metal-free photocatalysts so far.

NiSe-Ni0.85 Se Heterostructure Nanoflake Arrays on Carbon Paper as Efficient Electrocatalysts for Overall Water Splitting.

Fabricating cost-effective, bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in basic media is critical for renewable energy generation. Here, NiSe/CP, Ni0.85 Se/CP, and NiSe-Ni0.85 Se/CP heterostructure catalysts with different phase constitutions are successfully prepared through in situ selenylation of a NiO nanoflake array oriented on carbon paper (CP) by tuning the original Ni/Se molar ratio of the raw materials. The relationship between the crystal phase component and electrocatalytic activity is systematically studied. Benefiting from the synergetic effect of the intrinsic metallic state, facile charge transport, abundant catalytic active sites, and multiple electrolyte transmission paths, the optimized NiSe-Ni0.85 Se/CP exhibits a remarkably higher catalytic activity for both the HER and OER than single-phase NiSe/CP and Ni0.85 Se/CP. A current density of 10 mA cm-2 at 1.62 V and a high stability can be obtained by using NiSe-Ni0.85 Se/CP as both the cathode and anode for overall water splitting under alkaline conditions. Density functional theory calculations confirm that H and OH- can be more easily adsorbed on NiSe-Ni0.85 Se than on NiSe and Ni0.85 Se. This study paves the way for enhancing the overall water splitting performance of nickel selenides by fabricating heterophase junctions using nickel selenides with different phases.

Square-Root Sigma-Point Information Consensus Filters for Distributed Nonlinear Estimation.

This paper focuses on the convergence rate and numerical characteristics of the nonlinear information consensus filter for object tracking using a distributed sensor network. To avoid the Jacobian calculation, improve the numerical characteristic and achieve more accurate estimation results for nonlinear distributed estimation, we introduce square-root extensions of derivative-free information weighted consensus filters (IWCFs), which employ square-root versions of unscented transform, Stirling's interpolation and cubature rules to linearize nonlinear models, respectively. In addition, to improve the convergence rate, we introduce the square-root dynamic hybrid consensus filters (DHCFs), which use an estimated factor to weight the information contributions and shows a faster convergence rate when the number of consensus iterations is limited. Finally, compared to the state of the art, the simulation shows that the proposed methods can improve the estimation results in the scenario of distributed camera networks.

Visible-Light-Induced Self-Cleaning Property of Bi2Ti2O7-TiO2 Composite Nanowire Arrays.

Bi2Ti2O7-TiO2 composite nanowire arrays were prepared via a two-step sequential solvothermal and subsequent calcination process. The morphology and structure of the Bi2Ti2O7-TiO2 composite nanowire array composite were characterized by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. The UV-visible diffuse reflectance spectroscopy analysis indicated that the absorption spectrum of the Bi2Ti2O7-TiO2 composite nanowire array composite was extended to the visible-light region due to the existence of Bi2Ti2O7. The Bi2Ti2O7-TiO2 composite nanowire arrays exhibit superhydrophilicity with water contact angles of 0° after irradiation with visible light, and the superhydrophilic nature is retained for at least 15 days. This effect enables us to consider self-cleaning applications that do not require permanent UV exposure. Compared to pure Bi2Ti2O7 and TiO2, the vertically aligned Bi2Ti2O7-TiO2 composite nanowire arrays showed more significant visible-light self-cleaning performance due to the synergistic effect of superhydrophilicity and significant photocatalytic activity caused by effective electron-hole separation at the interfaces of the two semiconductors, which was confirmed by the electrochemical analysis and surface photovoltage technique.

Well-dispersed CoS nanoparticles on a functionalized graphene nanosheet surface: a counter electrode of dye-sensitized solar cells.

With a facile electrophoretic deposition and chemical bath process, CoS nanoparticles have been uniformly dispersed on the surface of the functionalized graphene nanosheets (FGNS). The composite was employed as a counter electrode of dye-sensitized solar cells (DSSCs), which yielded a power conversion efficiency of 5.54 %. It is found that this efficiency is higher than those of DSSCs based on the non-uniform CoS nanoparticles on FGNS (4.45 %) and built on the naked CoS nanoparticles (4.79 %). The achieved efficiency of our cost-effective DSSC is also comparable to that of noble metal Pt-based DSSC (5.90 %). Our studies have revealed that both the exceptional electrical conductivity of the FGNS and the excellent catalytic activity of the CoS nanoparticles improve the conversion efficiency of the uniformly FGNS-CoS composite counter electrode. The electrochemical impedance spectra, cyclic voltammetry, and Tafel polarization have evidenced the best catalytic activity and the fastest electron transport. Additionally, the dispersion condition of CoS nanoparticles on FGNS plays an important role for catalytic reduction of I3 (-) .

Surface tuning for oxide-based nanomaterials as efficient photocatalysts.

Due to the increasingly polluted environment and the gradual depletion of fossil fuel reserves, the development of renewable technologies for environmental remediation and energy production is highly desirable. Over the past decades, oxide-based semiconductor photocatalysis has attracted much attention. On various frontiers for efficient photocatalysis, surface-tuning strategies for synthesis and modification of oxides on the nanometer scale have progressed at a fast pace. Hence, it is of significance to review recent advances in the development of surface tuning for oxide-based nanomaterials as activity-enhanced photocatalysts. In this review, special emphases, especially for recent advances in our group, are given to surface tuning of novel nanocrystallites for high thermal stability, hierarchical structure assembly, heterojunctional nanocomposites and high-energy-facet exposure, along with effective testing tools for photogenerated charge properties at the surfaces and/or interfaces. This is of great significance for fields related to energy and environment from scientific and engineering viewpoints.

Novel defect-transit dual Z-scheme heterojunction: Sulfur-doped carbon nitride nanotubes loaded with bismuth oxide and bismuth sulfide for efficient photocatalytic amine oxidation.

The rational design of Z-scheme heterojunction hybrid photocatalysts is considered a promising way to achieve high photocatalytic activity. In this study, a dual Z-scheme heterojunction with bismuth sulfide (Bi2S3) nanorods and bismuth oxide (Bi2O3) nanoparticles anchored Sulfur-doped carbon nitride (S-CN) nanotubes (Bi2S3/S-CN/Bi2O3) is designed and fabricated through the ordinal metal ion adsorption, pyrolysis, and sulfidation processes using supramolecular rods as precursor. Compared with pristine Bi2S3, Bi2O3, and CN, the dual Z-scheme tube-shaped Bi2S3/S-CN/Bi2O3 catalyst exhibited a significantly improved photocatalytic activity in amine oxidation. The optimized Bi2S3/S-CN/Bi2O3 nanostructure exhibits a 97.6 % benzylamine conversion and 99.4 % imine selectivity within 4 h under simulated solar light irradiation. The excellent activity of Bi2S3/S-CN/Bi2O3 nanotubes can be attributed to the characteristic hollow defect band structure and efficient charge separation and transfer achieved by the dual Z-scheme charge transfer mechanism, which was systematically studied using electron spin resonance spectroscopy, Kelvin probe force microscope, and other techniques. The optimized dual Z-scheme heterojunction hybrid photocatalyst maintains the high oxidizing ability of Bi2S3 and Bi2O3 and the excellent reducing ability of CN, thereby significantly enhancing the photocatalytic activity. This research provides a facile and feasible synthesis strategy for designing dual Z-scheme heterojunctions with defect band structure to improve the photocatalytic activity.

Task-Oriented Robot Cognitive Manipulation Planning Using Affordance Segmentation and Logic Reasoning.

The purpose of task-oriented robot cognitive manipulation planning is to enable robots to select appropriate actions to manipulate appropriate parts of an object according to different tasks, so as to complete the human-like task execution. This ability is crucial for robots to understand how to manipulate and grasp objects under given tasks. This article proposes a task-oriented robot cognitive manipulation planning method using affordance segmentation and logic reasoning, which can provide robots with semantic reasoning skills about the most appropriate parts of the object to be manipulated and oriented by tasks. Object affordance can be obtained by constructing a convolutional neural network based on the attention mechanism. In view of the diversity of service tasks and objects in service environments, object/task ontologies are constructed to realize the management of objects and tasks, and the object-task affordances are established through causal probability logic. On this basis, the Dempster-Shafer theory is used to design a robot cognitive manipulation planning framework, which can reason manipulation regions' configuration for the intended task. The experimental results demonstrate that our proposed method can effectively improve the cognitive manipulation ability of robots and make robots preform various tasks more intelligently.

Robot gaining robust pouring skills through fusing vision and audio.

In the pouring task of service robots, the robust and accurate estimate of liquid height is a crucial step. However, neither vision nor audio alone can achieve better liquid height estimation. We instead propose a visual-audio information fusion network to enable robots with good pouring skills. Visual and audio information are used as information sources. Firstly, visual features are extracted by residual network based on attention model. Secondly, the Fourier characteristic matrix of audio information is obtained by fast Fourier transform, and then the audio feature is extracted by long-short term memory. Thirdly, visual features and audio features are fused by fully connected network to output the liquid height and state of the cup. Finally, a sinusoidal and transient fusion control method is proposed, which takes the liquid height and cup state as inputs, outputs the angle of the gripper, and provides an implementation method for the pouring task. Experiments are carried out to evaluate the performance of multimodal information fusion method and verify the effectiveness of the algorithm for pouring tasks of service robots.

Enhanced charge transfer and photocatalytic carbon dioxide reduction of copper sulphide@cerium dioxide p-n heterojunction hollow cubes.

Hollow structure hybrids have gained considerable attention for their ability to reduce CO2 owing to their rich active sites, high gas adsorption ability, and excellent light utilization capacity. Herein, a template-engaged strategy was provided to fabricate copper sulphide@cerium dioxide (CuS@CeO2) p-n heterojunction hollow cube photocatalysts using Cu2O cubes as a sacrificial template. The sequential steps of loading of CeO2 nanolayer, sulfidation, and etching reaction facilitate the formation of CuS@CeO2 p-n heterojunction hollow cubes. Compared with the single CuS, CeO2, and their physical mixture, the CuS@CeO2 p-n heterojunction hollow cube photocatalyst expresses a higher performance toward photocatalytic CO2 reduction under solid-gas reaction conditions due to the faster separation of photogenerated charges. The further enhanced performance of CuS@CeO2 p-n heterojunction hollow cubes was achieved by decorating pt nanoparticles due to the fact that Pt nanoparticles had a high electron affinity and CO2 adsorption capacity, and the highest CO and CH4 yields of the optimized hybrid reached 195.8 µmol g-1 h-1 and 19.96 µmol g-1 h-1, respectively. This work might provide a strategy for designing and synthesizing efficient hollow heterostructured photocatalysts for solar energy conversion and utilization.

Hierarchical S-scheme titanium dioxide@cobalt-nickel based metal-organic framework nanotube photocatalyst for selective carbon dioxide photoreduction to methane.

Efficient photocatalysts are of great importance for the photochemical conversion of CO2 into fuels. Herein, S-scheme titanium dioxide@cobalt-nickel based metal-organic framework (TiO2@CoNi-MOF) heterojunction photocatalysts with high surface area and porosity are designed and fabricated by a multi-step controllable strategy. The photocatalytic activity of the composites can be optimized by adjusting the loading content of CoNi-MOF in TiO2@CoNi-MOF and molar ratios of Co2+ and Ni2+ in CoNi-MOF. The optimized hybrid photocatalyst showed a much higher CO2 photoreduction activity than the control single-component samples (TiO2 and CoNi-MOF) with a high CH4 yield (41.65 µmol g-1 h-1) and selectivity (93.2%). The accelerated charge carrier separation induced by the S-scheme heterojunction significantly promoted the photocatalytic performance of TiO2@CoNi-MOF NTs. Meanwhile, the introduction of bimetallic CoNi-MOF nanosheets significantly resulted in the increase of active sites, CO2 adsorbability, visible-light utilization, and CH4 selectivity. Moreover, the S-scheme photoinduced charge transfer model of the TiO2@CoNi-MOF NTs photocatalyst was confirmed by photoluminescence spectroscopy, free radical trapping tests, and work function calculated from Kelvin probe. The work aims to design and fabricate heterojunction photocatalysts with high efficiency for solar fuel production.

Structure and properties of noncrystalline nano-Al(OH)3 reclaimed from carbonized residual wastewater treatment sludge.

Performance of wastewater treatement sludge-carbon (SC) can be evidently improved by removing the inorganic fractions. A novel investigation for recovery of Al from acid leaching of SC and synthesis of nano-Al(OH)(3) has been conducted. Results show that the sodium aluminates with high purity can be obtained by effectively dissolving the inorganic fractions from SC and by further removing the impurities (Fe(3+), Ca(2+), Mg(2+), S(4+), and P(3+)). Highly dispersed Al(OH)(3) with high S(BET) is obtained at pH = 6. The peaks of -CH(2)- vibration and the C1s peaks (binding energies of 284.6 eV) imply that polyethylene glycol 1000 (PEG-1000) is chemically adsorbed on the surface of Al(OH)(3) samples, which is propitious to reduce the hydrogen bonds between water molecules and surface -OH groups to prevent hard agglomeration. The stretching vibration peaks of [AlO(2)](-) and the Na1s peaks confirm that a trace of sodium aluminate (NaAl(OH)(4), Na(+)(H(2)O)(4)[Al(OH)(4)(-)], or the dehydrated monomers) is retained in the prepared Al(OH)(3). The main phase transformation for calcination (≤800 °C) of the SC-derived Al(OH)(3) is from amorphous Al(OH)(3) to amorphous A1(2)O(3). Here we highlight that production of Al(OH)(3) and SC from sludge provides the potential application in significant quantities that can revolutionize the handling of such kinds of harmful waste.

Fabrication of size-controlled hierarchical ZnS@ZnIn2S4 heterostructured cages for enhanced gas-phase CO2 photoreduction.

Designing and constructing advanced heterojunction architectures are desirable for boosting CO2 photoreduction performance of semiconductor photocatalysts. Herein, we have prepared hierarchical ZnS@ZnIn2S4 core-shell cages with controlled particle sizes using sequential synthesis of Zeolitic imidazolate (ZIF-8) polyhedrons, ZnS cages, and ZnIn2S4 nanosheets on the ZnS polyhedron cages. ZIF-8 polyhedrons are firstly synthesized by a liquid-phase approach. The subsequent sulfidation of the ZIF-8 polyhedrons results in the formation of ZnS polyhedron cages, which act as substrates for fabricating ZnS@ZnIn2S4 core-shell cages by growing ZnIn2S4 nanosheets. The size of ZnS cages can be tuned to optimize CO2 photoreduction performance of hierarchical ZnS@ZnIn2S4 core-shell cages. The synergy of the unique hierarchical core-shell cage-like structure and heterojunction composition endows the hybrid catalyst high incident light utilization, abundant active sites, and effective separation of photoexcited charge carriers. Benefiting from these advantages, the optimized hierarchical ZnS@ZnIn2S4 core-shell cages exhibit enhanced performance for CO2 photoreduction with the CO yield of 87.43 µmol h-1g-1 and 84.3% selectivity, which are much superior to those of single ZnIn2S4 or ZnS. Upon Au decoration, the CO2 photoreduction performance of ZnS@ZnIn2S4 core-shell cages is further enhanced because of the Schottky junctions and surface plasmon resonance effect.

Efficient charge transfer in cadmium sulfide quantum dot-decorated hierarchical zinc sulfide-coated tin disulfide cages for carbon dioxide photoreduction.

Constructing hybrid photocatalysts with advanced structures and controllable compositions is a promising way to improve CO2 photoreduction performance. In this work, SnS2 nanosheets are grown on ZnS polyhedron cages to fabricate hierarchical ZnS@SnS2 double-shelled heterostructured cages. This design integrates ZnS cages and SnS2 nanosheets into a stable heterostructured hybrid catalyst with a hierarchical double-shelled cage-like architecture, possessing abundant active sites, quick charge separation/migration, and high CO2 adsorption capacity. Benefiting from these advantages, the optimized hierarchical ZnS@SnS2 heterostructured cages exhibit significant gas-phase CO2 photoreduction activity with a CO generation rate of 95.38 µmol g-1h-1 and 72.4% CO selectivity, which are greatly improved in comparison with those of pure ZnS cages and nanosheet-assembled SnS2 particles. Furthermore, charge carrier separation efficiency and visible light harvesting ability are further improved by constructing a ZnS@SnS2/CdS type-I/type-II complex heterostructured system through surface decoration of CdS quantum dots. The optimized ZnS@SnS2/CdS hybrid exhibits a CO generation rate of 155.57 µmol g-1h-1 and an excellent selectivity of 80.4%. This work is conducive to the design and manufacture of advanced hybrids for solar energy utilization and photocatalytic reactions.

Sandwich-Structured Hybrid of NiCo Nanoparticles-Embedded Carbon Nanotubes Grafted on C3N4 Nanosheets for Efficient Photodehydrogenative Coupling Reactions.

Exploring cheap and efficient hybrid catalysts offers exciting opportunities for enhancing the performance of photocatalysts in the green organic synthesis field. Herein, a facile and effective approach is designed for the synthesis of a sandwich-structured hybrid in which NiCo bimetallic nanoparticles are embedded in the tip of nitrogen-doped carbon nanotubes (N-CNTs) grafted on both sides of a nitrogen deficient C3N4 (Nv-C3N4) nanosheet for photodehydrogenative coupling reactions. Such a brand-new type of sandwich-structured hybrid comprises Nv-C3N4 nanosheets and surrounding N-CNTs embedded with NiCo nanoparticles at their tips. Remarkably, the resultant hybrid exhibits integrated functionalities, abundant active sites, enhanced visible light absorption, and excellent interfacial charge transfer ability. As a result, the optimized NiCo@N-CNTs@Nv-C3N4 photocatalyst shows significantly improved photodehydrogenative coupling performance of amines to imines compared to the control single-metal-based catalysts (Ni@N-CNTs@Nv-C3N4 and Co@N-CNTs@Nv-C3N4). The mechanistic investigation through experimental and computational study demonstrates that, compared with single-metal-based hybrids, the NiCo bimetallic hybrid exhibits stronger amine adsorption and weaker photogenerated hydrogen atom adsorption, thus promoting the dehydrogenative activation of primary amines and fast generation of imines. This work presents a promising insight for designing and preparing efficient photocatalysts to trigger organic synthesis in high yields.

Multi-channel charge transfer of hierarchical TiO2 nanosheets encapsulated MIL-125(Ti) hollow nanodisks sensitized by ZnSe for efficient CO2 photoreduction.

Metal-organic frameworks-based hybrids with desirable components, structures, and properties have been proven to be promising functional materials for photocatalysis and energy conversion applications. Herein, we proposed and prepared ZnSe sensitized hierarchical TiO2 nanosheets encapsulated MIL-125(Ti) hollow nanodisks with sandwich-like structure (MIL-125(Ti)@TiO2\ZnSe HNDs) through a successive solvothermal and selenylation reaction route using the as-prepared MIL-125(Ti) nanodisks as precursor. In the ternary MIL-125(Ti)@TiO2\ZnSe HNDs hybrid, TiO2 nanosheets were transformed from MIL-125(Ti) and in situ grown on both sides of the MIL-125(Ti) shell, forming sandwich-like hollow nanodisks, and the ratio of MIL-125(Ti)/TiO2 can be tuned by changing the solvothermal time. The ternary hybrids possess the advantages of enhanced incident light utilization and abundant accessible active sites originating from bimodal pore-size distribution and hollow sandwich-like heterostructure, which can effectively promote CO2 photoreduction reaction. Especially, the formed multi-channel charge transfer routes in the ternary heterojunctions contribute to the charge transfer/separation and extend the lifespan of charge-separated state, thus boosting CO2 photoreduction performance. The CO (513.1 µmol g-1h-1) and CH4 (45.1 µmol g-1h-1) evolution rates over the optimized ternary hybrid were greatly enhanced compared with the single-component and binary hybrid photocatalysts.

Hierarchical CuS@ZnIn2S4 Hollow Double-Shelled p-n Heterojunction Octahedra Decorated with Fullerene C60 for Remarkable Selectivity and Activity of CO2 Photoreduction into CH4.

In this work, a hollow double-shelled architecture, based on n-type ZnIn2S4 nanosheet-coated p-type CuS hollow octahedra (CuS@ZnIn2S4 HDSOs), is designed and fabricated as a p-n heterojunction photocatalyst for selective CO2 photoreduction into CH4. The resulting hybrids provide rich active sites and effective charge migration/separation to drive CO2 photoreduction, and meanwhile, CO detachment is delayed to increase the possibility of eight-electron reactions for CH4 production. As expected, the optimized CuS@ZnIn2S4 HDSOs manifest a CH4 yield of 28.0 µmol g-1 h-1 and a boosted CH4 selectivity up to 94.5%. The decorated C60 both possesses high electron affinity and improves catalyst stability and CO2 adsorption ability. Thus, the C60-decorated CuS@ZnIn2S4 HDSOs exhibit the highest CH4 evolution rate of 43.6 µmol g-1 h-1 and 96.5% selectivity. This work provides a rational strategy for designing and fabricating efficient heteroarchitectures for CO2 photoreduction.

Improved charge separation and carbon dioxide photoreduction performance of surface oxygen vacancy-enriched zinc ferrite@titanium dioxide hollow nanospheres with spatially separated cocatalysts.

Here, we describe the fabrication of surface oxygen vacancy-enriched ZnFe2O4@TiO2 double-shell hollow heterostructure nanospheres (ZnFe2O4@H-TiO2-x) coupled with spatially separated CoOx and Au-Cu bimetallic cocatalysts. The ZnFe2O4@TiO2 heterojunction and spatially separated dual cocatalysts can significantly promote the separation of photoinduced charge carriers. Combined with the unique hollow double-shell heterostructure characteristics and improved surface state properties, the hybrid nanospheres can efficiently adsorb and activate CO2 molecules. These advantages cause the optimized catalyst to exhibit remarkably higher gas-phase photocatalytic CO2 reduction activity than the control CoOx/ZnFe2O4/Au-Cu and ZnFe2O4@H-TiO2-x double-shell hollow nanospheres loaded with a single cocatalyst. Meanwhile, the Au-Cu bimetal effect boosts the CO2 conversion rate and CH4 selectivity. The optimized hybrid catalyst with a Au/Cu ratio of 1:1 provides a CH4 yield of 21.39 µmol g-1 h-1 with 93.8% selectivity. This work provides a rational photocatalyst design to improve CO2 conversion and CH4 selectivity.