Collection of Carbon Neutrality(202312)
In this study, one-dimensional single-crystal TiO2 nanobelt arrays with surface oxygen vacancies were constructed by Pd-catalyzed oxygen reduction method in anoxic environment to address the problems of insufficient surface active sites and slow reaction kinetics of TiO2, low yield and poor selectivity of hydrocarbons in CO2 reduction products. The effects of surface oxygen vacancies and hydrogen spillover of Pd on the separation and transport of photogenerated carrier and the selectivity of reduction product were investigated from morphological structure, carrier behavior and photocatalytic performance. With high CO2 reduction activity of Pd-Ov-TNB, yields of CH4, C2H6 and C2H4 are 40.8, 32.09 and 3.09 µmol·g-1·h-1, respectively, and selectivity of hydrocarbons is as high as 84.52%, showing great potential in C-C coupling. Its excellent photocatalytic activity is attributed to the one-dimensional single-crystal nanobelt structure that increases the active specific surface area and crystallinity of the material, provides more active sites for the CO2 reduction and accelerates the segregated transport of photogenerated charges. Meanwhile, the oxygen vacancies enhance the surface accumulation of photogenerated charges, providing an electron-rich environment for CO2 reduction. In addition, Pd nanoparticles increase concentration of H* in the reaction system, and then transfer H* to active sites of CO2 adsorption on the catalyst surface through the hydrogen spillover effect, promoting the hydrogenation of reaction intermediates. Comprehensive advantages of Pd-nanoparticals contribute to the efficient conversion of CO2 to hydrocarbons.
Cu/Mg-MOF-74 has several advantages, such as high specific surface area, adjustable microporous structure, alkali metal active site, excellent CO2 adsorption, and good photocatalytic activity. However, how the molar ratio of Cu/Mg (Cu/Mg ratio) affects its CO2 adsorption selectivity in a simulated flue gas is still unclear. Here, a synthesized Cu/Mg-MOF-74, with series of Cu/Mg ratios, using the solvothermal method was analyzed about its CO2 photocatalytic performance, CO2 and N2 uptake, and pore structure. The CO2 adsorption selectivity was calculated to reveal the effect of Cu/Mg ratio on CO2 and N2 uptake and selectivity. The results indicate that the photocatalytic activity of Cu/Mg-MOF-74 for CO2 reduction to CO and H2 initially increases and then decreases with Cu/Mg ratio decreasing. At the Cu/Mg ratio of 0.6/0.4, the yield of CO and H2 by photocatalytic reduction is the highest, showing up to 10.65 and 5.41 μmol·h−1·gcat−1 (1 MPa, 150 ℃), respectively. Furthermore, CO2 and N2 uptakes of Cu/Mg-MOF-74 increase as the Cu/Mg ratio decreases, and the increase in CO2 uptake is more pronounced. At the Cu/Mg ratio of 0.1/0.9, the CO2 and N2 uptakes are the largest, reaching 9.21 and 1.49 mmol·g−1 (273.15 K, 100 kPa), respectively. Their area and volume of micropore (d1 ≥ 0.7 nm) and ultramicropore (d2 < 0.7 nm) increase as the Cu/Mg ratio decreases. At the Cu/Mg ratio of 0.22/0.78, the area and volume of micropores and ultramicropores are larger than those of Mg-MOF-74. The selectivity of Cu/Mg-MOF-74 increases correspondingly with Cu/Mg ratio decreasing and CO2 concentration increasing. CO2 adsorption on Cu/Mg-MOF-74 is a combination process of pore-filling and Mg2+ chemical adsorption in which the micropore volume is the key factor affecting its adsorption performance. All above data demonstrate that modulating the Cu/Mg ratio can promisingly regulate the pore structure of Cu/Mg-MOF-74, CO2 uptake, and selectivity.
One of the basic challenges of CO2 photoreduction is to develop efficient photocatalysts. As an effective strategy, constructing heterostructure photocatalysts with intimate interfaces can enhance interfacial charge transfer for realizing high photocatalytic activity. Herein, a novel photocatalytic material, Bi4O5Br2/CeO2 composite fiber (B@C-x, x refers to the amount of reactant), was constructed by embeding CeO2 nanofibers on Bi4O5Br2 nanosheets via an electrospinning combined with hydrothermal method. Its composition, morphology and photoelectric properties were characterized. The results show that Bi4O5Br2/CeO2 heterojunction with appropriate Bi4O5Br2 content can significantly improve the photocatalytic performance of CeO2 nanofibers. Compared with pure Bi4O5Br2 and CeO2, B@C-2 exhibited the best photocatalytic activity under simulated sunlight. The Bi4O5Br2/CeO2 exhibited improved photocatalytic CO2 reduction performance with a CO generation rate of 8.26 μmol·h−1·g−1 without using any sacrificial agents or noble co-catalysts. This can be attributed to the tight interfacial bonding between Bi4O5Br2 and CeO2 and the formation of S-scheme heterojunction, which enables the efficient spatial separation and transfer of photogenerated carriers. This work provides a simple and efficient method for directional synthesis of Bi-based photocatalytic composites with S-scheme heterojunction and illustrates an applicable tactic to develop potent photocatalysts for clean energy conversion.
The conversion of CO2 into high value-added chemicals is an effective way to realize the carbon cycle, alleviate energy crisis and environmental problems. The preparation of metal-semiconductor electrodes provides a new idea for CO2 conversion by photoelectric coupling technology. In this study, Si was etched in alkali solution, on which a bimetallic Bi, Zn co-modified Si photoelectrocathode (BiZnx/Si) was prepared via the electrodeposition process, for the photoelectrochemical reduction CO2. The results show that the introduction of Bi and Zn can improve the light absorption performance, reduce the electrochemical impedance, and increase the electrochemical active surface area (ECSA). Especially, the ECSA of the best photoelectrocathode BiZn2/Si is 0.15 mF·cm-2. Besides, the cooperative effect of Bi and Zn can improve the adsorption performance toward the intermediates *OCHO. During the photoelectrochemical reduction of CO2, the Faradaic efficiency for HCOOH reaches up to 96.1% on the best photoelectrocathode BiZn2/Si at the potential of -0.8 V (vs. RHE). Moreover, the photocurrent intensity on the photoelectrocathode BiZn2/Si remained -13 mA·cm-2 during the 10 h photoelectric stability test, suggesting its high stability.
Since the beginning of the 21st century, energy shortage and environmental pollution have been the major challenges faced by human beings. Photocatalytic carbon dioxide (CO2) reduction is one of the promising strategies to solve the energy crisis and promote the carbon cycle, in which semiconductor captures solar energy to obtain hydrocarbon fuel. However, the low activity and poor selectivity of the products greatly limit the practical application of this technology. Thus, it is of great significance to regulate product selectivity, improve photocatalytic efficiency, and deeply understand the mechanism of CO2 reduction reaction. In recent years, ultrathin materials have attracted extensive attention from researchers due to their high specific surface area, abundant unsaturated coordination surface atoms, shortened charge migration path from inside to surface, and tailorable energy band structure, and have achieved promising results in the field of photocatalytic CO2 reduction. In this paper, the reaction mechanism of photocatalytic CO2 reduction is firstly summarized. Next, the research results of promoting electron hole separation and regulating charge transport path of ultrathin nanostructures by constructing heterostructures, designing Z-scheme systems, introducing co-catalysts, and defect engineering are introduced. Finally, the prospect and challenge of improving the efficiency of photocatalytic CO2 reduction and optimizing the product selectivity are pointed out.
Conversion of CO2 into fuels by photocatalysis is promising in solving the energy crisis and the greenhouse effect. Among various photocatalytic materials, Zn1-2x(CuGa)xGa2S4 materials possess visible light response and high conduction band potential, which are ideal CO2 reduction materials from thermodynamics aspect. However, their photocatalytic CO2 reduction activity is still low which is urgent to improve its activity in terms of kinetics. In this study, Zn0.4(CuGa)0.3Ga2S4 was synthesized and composited with CdS nanoparticles with different proportions to form Zn0.4(CuGa)0.3Ga2S4/CdS heterojunction photocatalysts. A series of characterizations suggest that CdS is uniformly grown on surface of Zn0.4(CuGa)0.3Ga2S4 microcrystals to form a Z-scheme type all-solid heterojunction composite materials. Such a structure effectively suppresses the recombination of electron-hole pairs and improve the photocatalytic performance. In the solution CO2 reduction system, the as-prepared Zn0.4(CuGa)0.3Ga2S4/CdS can effectively reduce CO2 into CO under visible light irradiation. The optimal molar ratio of Zn0.4(CuGa)0.3Ga2S4 and CdS in composite materials is 2 : 1, whose photocatalytic performance is 1.7 times of that of Zn0.4(CuGa)0.3Ga2S4/ CdS and 1.6 times of that of CdS. This work constructs all solid Z-scheme type Zn0.4(CuGa)0.3Ga2S4/CdS heterojunction materials with enhanced photocatalytic activity for CO2 reduction, which is promising for designing novel photocatalysts in field of artificial photosynthesis.
Highly light absorptive photocatalysts are of great significance to boost the photothermal conversion efficiency. Light trapping effect of nanoarray structured photothermal catalysts can enhance the light absorption and improve the photothermal conversion efficiency. However, the practical applications of array-based catalysts are hindered by very low loadings of active metal catalysts per unit illumination area. Herein, we develop a SiO2-protected MOFs pyrolysis method for the preparation of powder-form cobalt plasmonic superstructures that enable a 90% absorption efficiency of sunlight and tunable metal loading per unit area. Its high light absorption capacity was confirmed by time-domain finite-difference simulation calculations due to the plasmonic hybridization effect of nanoparticles. Compared with nanoarray-structured plasmonic superstructures, the powder-form catalyst exhibit enhanced catalytic activity and stability, resulting in the increase of CO2 conversion efficiency from 0.9% to 26.2%. This study lays the foundation for the practical application of non-precious metal photothermal catalysts.
The electrocatalytic carbon dioxide reduction reaction can convert the greenhouse gas carbon dioxide into chemical raw materials or organic fuels, providing a feasible way to overcome global warming and the conversion of electrical energy to chemical energy. The main challenge of this technology is the wide product distribution, resulting in low selectivity of a single product, however, modulating the surface properties of the catalyst is an efficient strategy to solve this problem. In this study, the precursors of Cu2O and Cu2S were oxidized to the CuO catalysts with different surface properties. The CuO-FS catalyst derived from Cu2S delivered the improved activity of electro-reduction of carbon dioxide and selectivity for formic acid product. This catalyst exhibited a higher total current density and the Faraday efficiency of formic acid > 70% in a wide test voltage range of -0.8 - -1.1 V; the Faraday efficiency for formic acid could reach a maximum of 78.4% at -0.9 V. The mechanism study indicated that the excellent performance of CuO-FS for electro-reduction of carbon dioxide could be attributed to the large electrochemically active surface area, which provided a large number of surface active sites, resulting in a higher total current density; moreover, the less zero-valent Cu was produced over the surface of CuO-FS during the electrocatalytic process, which reduced the production of ethylene and thus promoted the production of formic acid.