Realizing the high loading amount of active Cu on Al2O3 to boost its CO catalytic oxidation.

Catalytic oxidation of carbon monoxide (CO) by Cu/Al2O3 has garnered increasing interest in recent years due to its promising application prospects. Numerous investigations conducted on the Cu/Al2O3 system, but its catalytic performance for CO oxidation is still not as promising as that of precious metal catalysts. Increasing the loading amount of the active Cu on Al2O3 surface is a feasible method for improving its activity. However, with the increase of Cu loading, the agglomeration and enlargement of Cu particles is inevitable, which reduces the active Cu amount. Therefore, the utilization rate of Cu atoms is not high and the catalytic performance often can not further rise. Enhancing active Cu loading amount as high as possible is a prerequisite to further enlarge the activity of Cu/Al2O3 catalyst. Herein, self-synthesized Al2O3 nanofibers (Al2O3-nf) with high specific surface area and abundant penta-coordinated aluminum (AlV) are used as the support to maximize the Cu loading amount by chemical vapor deposition (CVD). And commercially available α-Al2O3 is used for comparative experiment. The high specific surface area could make Cu high dispersion on Al2O3, even at 20 wt% Cu loads, which is beneficial to high concentration load of active Cu. The catalytic activity of Cu/Al2O3-nf-CVD gradually increases with the increase of Cu loading from 2 wt% to 20 wt%, exhibiting a clear linear correlation with the surface content of Cu0 on the catalyst. Meanwhile, this result confirms that Cu0 plays a crucial role in CO oxidation of Cu/Al2O3. However, commercial α-Al2O3 reaches its highest activity when the Cu load is 5%, and then its activity begins to decrease due to the agglomeration of particles. Moreover, Cu/Al2O3-nf-CVD also exhibits remarkable thermal stability for CO oxidation. This work highlights a new strategy to synthesis of high Cu loading amount, high activity and thermostable Cu/Al2O3 catalyst for low-temperature oxidation of CO.

Constructing extrinsic oxygen vacancy on the surface of photocatalyst as CO2 and electrons reservoirs to improve photocatalytic CO2 reduction activity.

Constructing own oxygen vacancies in the photocatalysts is a very promising method to improve their photocatalytic CO2 reduction activity. However, some catalysts have excellent stabilities, making it difficult for them to construct their own oxygen vacancies. To simplify the above difficulty of stable photocatalysts, constructing extrinsic oxygen vacancies on their surface as a novel idea is proposed. Here, a stable TiO2 nanosheet is chosen as a research object, we uniformly deposited BiOCl quantum dots on their surface via a simple adsorption-deposition method. It is found that BiOCl quantum dots are able to simultaneously self-transform into defective BiOCl with many oxygen vacancies when the photocatalyst is performed photocatalytic CO2 reduction. These extrinsic oxygen vacancies can act as "CO2 and photo-generated electrons reservoirs" to improve CO2 capture and accelerate the separation of photogenerated electrons and holes. For the above reasons, the modified TiO2 showed obvious enhancement of photocatalytic CO2 reduction compared to pristine TiO2 and BiOCl. This work may open a new avenue to broaden the use of oxygen vacancies in the process of photocatalytic CO2 reduction.

Enhancing photocatalytic CO2 reduction with TiO2-based materials: Strategies, mechanisms, challenges, and perspectives.

The concentration of atmospheric CO2 has exceeded 400 ppm, surpassing its natural variability and raising concerns about uncontrollable shifts in the carbon cycle, leading to significant climate and environmental impacts. A promising method to balance carbon levels and mitigate atmospheric CO2 rise is through photocatalytic CO2 reduction. Titanium dioxide (TiO2), renowned for its affordability, stability, availability, and eco-friendliness, stands out as an exemplary catalyst in photocatalytic CO2 reduction. Various strategies have been proposed to modify TiO2 for photocatalytic CO2 reduction and improve catalytic activity and product selectivity. However, few studies have systematically summarized these strategies and analyzed their advantages, disadvantages, and current progress. Here, we comprehensively review recent advancements in TiO2 engineering, focusing on crystal engineering, interface design, and reactive site construction to enhance photocatalytic efficiency and product selectivity. We discuss how modifications in TiO2's optical characteristics, carrier migration, and active site design have led to varied and selective CO2 reduction products. These enhancements are thoroughly analyzed through experimental data and theoretical calculations. Additionally, we identify current challenges and suggest future research directions, emphasizing the role of TiO2-based materials in understanding photocatalytic CO2 reduction mechanisms and in designing effective catalysts. This review is expected to contribute to the global pursuit of carbon neutrality by providing foundational insights into the mechanisms of photocatalytic CO2 reduction with TiO2-based materials and guiding the development of efficient photocatalysts.

Recent Advances of Constructing Metal/Semiconductor Catalysts Designing for Photocatalytic CO2 Hydrogenation.

With the development of the world economy and the rapid advancement of global industrialization, the demand for energy continues to grow. The significant consumption of fossil fuels, such as oil, coal, and natural gas, has led to excessive carbon dioxide emissions, causing global ecological problems. CO2 hydrogenation technology can convert CO2 into high-value chemicals and is considered one of the potential ways to solve the problem of CO2 emissions. Metal/semiconductor catalysts have shown good activity in carbon dioxide hydrogenation reactions and have attracted widespread attention. Therefore, we summarize the recent research on metal/semiconductor catalysts for photocatalytic CO2 hydrogenation from the design of catalysts to the structure of active sites and mechanistic investigations, and the internal mechanism of the enhanced activity is elaborated to give guidance for the design of highly active catalysts. Finally, based on a good understanding of the above issues, this review looks forward to the development of future CO2 hydrogenation catalysts.

Applications of BiOX in the Photocatalytic Reactions.

BiOX (X = Cl, Br, I) families are a kind of new type of photocatalysts, which have attracted the attention of more and more researchers. The suitable band gaps and their convenient tunability via the change of X elements enable BiOX to adapt to many photocatalytic reactions. In addition, because of their characteristics of the unique layered structure and indirect bandgap semiconductor, BiOX exhibits excellent separation efficiency of photogenerated electrons and holes. Therefore, BiOX could usually demonstrate fine activity in many photocatalytic reactions. In this review, we will present the various applications and modification strategies of BiOX in photocatalytic reactions. Finally, based on a good understanding of the above issues, we will propose the future directions and feasibilities of the reasonable design of modification strategies of BiOX to obtain better photocatalytic activity toward various photocatalytic applications.

Light Control-Induced Oxygen Vacancy Generation and In Situ Surface Heterojunction Reconstruction for Boosting CO2 Reduction.

The weak adsorption of CO2 and the fast recombination of photogenerated charges harshly restrain the photocatalytic CO2 reduction efficiency. The simultaneous catalyst design with strong CO2 capture ability and fast charge separation efficiency is challenging. Herein, taking advantage of the metastable characteristic of oxygen vacancy, amorphous defect Bi2O2CO3 (named BOvC) was built on the surface of defect-rich BiOBr (named BOvB) through an in situ surface reconstruction progress, in which the CO32- in solution reacted with the generated Bi(3-x)+ around the oxygen vacancies. The in situ formed BOvC is tightly in contact with the BOvB and can prevent the further destruction of the oxygen vacancy sites essential for CO2 adsorption and visible light utilization. Additionally, the superficial BOvC associated with the internal BOvB forms a typical heterojunction promoting the interface carriers' separation. Finally, the in situ formation of BOvC boosted the BOvB and showed better activity in the photocatalytic reduction of CO2 into CO (three times compared to that of pristine BiOBr). This work provides a comprehensive solution for governing defects chemistry and heterojunction design, as well as gives an in-depth understanding of the function of vacancies in CO2 reduction.

Advances in the Application of Bi-Based Compounds in Photocatalytic Reduction of CO2.

Bi-based semiconductor materials have special layered structure and appropriate band gap, which endow them with excellent visible light response ability and stable photochemical characteristics. As a new type of environment-friendly photocatalyst, they have received extensive attention in the fields of environmental remediation and energy crisis resolution and have become a research hotspot in recent years. However, there are still some urgent issues that need to be addressed in the practical large-scale application of Bi-based photocatalysts, such as the high recombination rate of photogenerated carriers, limited response range to visible spectra, poor photocatalytic activity, and weak reduction ability. In this paper, the reaction conditions and mechanism of photocatalytic reduction of CO2 and the typical characteristics of Bi-based semiconductor materials are introduced. On this basis, the research progress and application results of Bi-based photocatalysts in the field of reducing CO2, including vacancy introduction, morphological control, heterojunction construction, and co-catalyst loading, are emphasized. Finally, the future prospects of Bi-based photocatalysts are prospected, and it is pointed out that future research directions should be focused on improving the selectivity and stability of catalysts, deeply exploring reaction mechanisms, and meeting industrial production requirements.

S-Scheme 2D/2D Heterojunction of ZnTiO3 Nanosheets/Bi2WO6 Nanosheets with Enhanced Photoelectrocatalytic Activity for Phenol Wastewater under Visible Light.

The pollution of phenol wastewater is becoming worse. In this paper, a 2D/2D nanosheet-like ZnTiO3/Bi2WO6 S-Scheme heterojunction was synthesized for the first time through a two-step calcination method and a hydrothermal method. In order to improve the separation efficiency of photogenerated carriers, the S-Scheme heterojunction charge-transfer path was designed and constructed, the photoelectrocatalytic effect of the applied electric field was utilized, and the photoelectric coupling catalytic degradation performance was greatly enhanced. When the applied voltage was +0.5 V, the ZnTiO3/Bi2WO6 molar ratio of 1.5:1 had highest degradation rate under visible light: the degradation rate was 93%, and the kinetic rate was 3.6 times higher than that of pure Bi2WO6. Moreover, the stability of the composite photoelectrocatalyst was excellent: the photoelectrocatalytic degradation rate of the photoelectrocatalyst remained above 90% after five cycles. In addition, through electrochemical analysis, XRD, XPS, TEM, radical trapping experiments, and valence band spectroscopy, we found that the S-scheme heterojunction was constructed between the two semiconductors, which effectively retained the redox ability of the two semiconductors. This provides new insights for the construction of a two-component direct S-scheme heterojunction as well as a feasible new solution for the treatment of phenol wastewater pollution.

Supercharged CO2 Photothermal Catalytic Methanation: High Conversion, Rate, and Selectivity.

To overcome the thermodynamic and kinetic impediments of the Sabatier CO2 methanation reaction, the process must be operated under very high temperature and pressure conditions, to obtain an industrially viable conversion, rate, and selectivity. Herein, we report that these technologically relevant performance metrics have been achieved under much milder conditions using solar rather than thermal energy, where the methanation reaction is enabled by a novel nickel-boron nitride catalyst. In this regard, an in situ generated HOB⋅⋅⋅B surface frustrated Lewis's pair is considered responsible for the high Sabatier conversion 87.68 %, reaction rate 2.03 mol gNi -1 h-1 , and near 100 % selectivity, realized under ambient pressure conditions. This discovery bodes well for an opto-chemical engineering strategy aimed at the development and implementation of a sustainable 'Solar Sabatier' methanation process.

Dealloying fabrication of hierarchical porous Nickel-Iron foams for efficient oxygen evolution reaction.

Designing and preparing highly active oxygen evolution reaction (OER) electrodes are essential for improving the overall efficiency of water splitting. Increasing the number of active sites is the simplest way to enhance OER performance. Herein, we present a dealloy-etched Ni-Fe foam with a hierarchical nanoporous structure as integrated electrodes with excellent performance for OER. Using the dealloying method on the Ni-Fe foam framework, a nanoporous structure is produced, which is named nanoporous Ni-Fe@Ni-Fe foam (NP-NF@NFF). Because of the peculiarities of the dealloying method, the NP-NF@NFF produced contains oxygen vacancies and heterojunctions. As a result, NP-NF@NFF electrode outperforms state-of-the-art noble metal catalysts with an extremely low overpotential of 210 and 285 mV at current densities of 10 and 100 mA cm-2, respectively. Additionally, the NP-NF@NFF electrode shows a 60-h stability period. Therefore, NP-NF@NFF provides new insights into the investigation of high-performance transition metal foam electrodes with effective active sites for efficient oxygen evolution at high current densities.

Building a Bridge from Papermaking to Solar Fuels.

Black liquor, an industrial waste product of papermaking, is primarily used as a low-grade combustible energy source. Despite its high lignin content, the potential utility of black liquor as a feedstock in products manufacturing, remains to be exploited. Demonstrated here in is the use of black liquor as a primary feed-stock for synthesizing graphene quantum dots that exhibit both up-conversion and photoluminescence when excited using visible/near-infrared radiation, thereby enabling the photosensitization of ultraviolet-absorbing TiO2 nanosheets. In addition, these graphene quantum dots can trap photo-generated electrons to realize the effective separation of electron-hole pairs. Together, these two processes facilitate the solar-powered generation of H2 from H2 O, and CO from H2 O-CO2 , using broadband solar radiation.

Living Atomically Dispersed Cu Ultrathin TiO2 Nanosheet CO2 Reduction Photocatalyst.

Supported atomically dispersed metals are proving to be efficacious photocatalysts for CO2 reduction to solar fuels. While being atom efficient, they suffer from being noble, rare, and costly (Pt, Pd, Au, Ag, Rh) and lacking in long-term stability. Herein, all of these problems are solved with the discovery that atomically dispersed Cu supported on ultrathin TiO2 nanosheets can photocatalytically reduce an aqueous solution of CO2 to CO. The atomically dispersed Cu can be recycled in a straightforward procedure when they become oxidatively deactivated. This advance bodes well for the development of a solar fuels technology founded on abundant, low-cost, nontoxic, atomically dispersed metal photocatalysts.

One-Pot Solvothermal Synthesis of Bi4V2O11 as A New Solar Water Oxidation Photocatalyst.

Bi4V2O11 was prepared via a one-pot solvothermal method and characterized via XRD, Raman, XPS, Electrochemical impedance spectroscopy. The as-prepared Bi4V2O11 sample displays excellent photocatalytic activity towards oxygen evolution under light irradiation. The hierarchical structure is in favour of the spatial separation of photogenerated electrons and holes. Furthermore, the internal polar field also plays a role in improving the charge separation. Both of the two results are responsible for excellent activity of O2 evolution. The resulting hierarchical Bi4V2O11 sample should be very promising photocatalyst for the application of photocatalytic O2 evolution in the future.

One-step synthesis of amorphous silver silicates with tunable light absorption spectra and photocatalytic activities in the visible region.

A series of amorphous silver silicates with different compositions were synthesized for the first time by one-step co-precipitation. Silicate ions were found to have important role on determining visible light absorption and photocatalytic activities of amorphous silver silicates, and the sample with Ag/Si ratio of 3.20 exhibits optimal photocatalytic activity.

Immobilization of BiOX (X = Cl, Br) on activated carbon fibers as recycled photocatalysts.

BiOX have been grown on the surface of activated carbon fibers (ACF) as recycled photocatalysts. The analysis results illustrate that electrostatic adsorption plays an important role in the formation of BiOX/ACF composites. The photocatalytic experimental results indicate that BiOX/ACF show excellent cyclic properties and stable performance.