Photoreduction Activity Research Articles

Facet-Dependent Photocatalytic CO2 Reduction on TiO2 Crystals in the Presence of SO2: Role of Surface Hydroxyl.

Photocatalytic CO2 reduction to solar energy makes great sense to mitigate the greenhouse effect caused by CO2, and great efforts have been made to promote CO2 conversion efficiency. However, the effect of impurities in the photoreduction of CO2 has received relatively little attention. Here, the different CO2 photoreduction behaviors of TiO2 exposed (101) facet (TiO2-101) and (001) facet (TiO2-001) with an SO2 impurity were investigated. On TiO2-101, SO2 accelerates the deactivation of the catalyst for CO2 photoreduction activity, since SO2 mainly binds to the OHb site of TiO2-101. This site is highly susceptible to the transfer of photogenerated holes, resulting in the rapid generation of SO42-, which occupies the active site and poisons the catalyst. For TiO2-001, SO2 has relatively little negative effect on stability, as SO2 mainly binds to the weak binding site (OHt) of TiO2-001, preventing it from being oxidized to SO42-, which alleviates catalyst deactivation and ensures the continuity of CO2 reduction. This paper provides further insights into the role of SO2 in CO2 photoreduction over distinct TiO2 facets and reveals the importance of facet engineering in the photocatalytic reduction of CO2 from industrial flue gas.

Enhanced photocatalytic synthesis of urea from co‐reduction of N2 and CO2 on Z‐schematic SrTiO3‐FeS‐CoWO4 heterostructure

The photocatalytic co‐reduction of CO2 and N2 is a sustainable method for urea synthesis under mild conditions. However, high‐yield synthesis of urea is a challenge due to the sluggish kinetics of the C‐N coupling reaction. Herein, we have successfully engineered a Z‐scheme photocatalyst, SrTiO3‐FeS‐CoWO4, for boosting photocatalytic urea synthesis via enhancing the initial CO2 and N2 adsorption step and reducing the energy barrier for the C‐N coupling reaction. A high urea yield of 8054.2 μg·gcat−1·h‐1 was achieved on SrTiO3‐FeS‐CoWO4, which was significantly higher than the state‐of‐the‐art. The SrTiO3‐FeS‐CoWO4 Z‐scheme photocatalyst, with accelerated charge transfer by FeS, not only had dual active sites for the chemical adsorption and activation of CO2 and N2, but also retained the high conduction band (‐1.50 eV) and accelerated supply of electrons and protons, which are responsible for its good photoreduction activity and significantly reduced energy barrier for the rate‐determining step of C‐N coupling reaction.

Enhanced Photocatalytic Synthesis of Urea from co-Reduction of N2 and CO2 on Z-Schematic SrTiO3-FeS-CoWO4 Heterostructure.

The photocatalytic co-reduction of CO2 and N2 is a sustainable method for urea synthesis under mild conditions. However, high-yield synthesis of urea is a challenge due to the sluggish kinetics of the C-N coupling reaction. Herein, we have successfully engineered a Z-scheme photocatalyst, SrTiO3-FeS-CoWO4, for boosting photocatalytic urea synthesis via enhancing the initial CO2 and N2 adsorption step and reducing the energy barrier for the C-N coupling reaction. A high urea yield of 8054.2 μg ⋅ gcat -1 ⋅ h-1 was achieved on SrTiO3-FeS-CoWO4, which was significantly higher than the state-of-the-art. The SrTiO3-FeS-CoWO4 Z-scheme photocatalyst, with accelerated charge transfer by FeS, not only had dual active sites for the chemical adsorption and activation of CO2 and N2, but also retained the high conduction band (-1.50 eV) and accelerated supply of electrons and protons, which are responsible for its good photoreduction activity and significantly reduced energy barrier for the rate-determining step of C-N coupling reaction.

Influence of Rapid Heat Treatment on the Photocatalytic Activity and Stability of Barium Titanates Against a Broad Range of Pollutants.

Barium titanate photocatalysts were synthesized via a sol-gel method involving a unique, cost-effective calcination technique that includes rapid heating and short exposure. The samples were characterized by X-ray diffractometry, scanning electron microscopy, diffuse reflectance spectroscopy, photoluminescence spectroscopy, infrared spectroscopy, and nitrogen adsorption-desorption measurements. The photooxidation activity and stability of the samples were evaluated by the degradation of phenol, oxalic acid, and chlorophenol. Their photoreduction activity was also investigated by the photocatalytic conversion of CO2 to CO. In both cases, UV irradiation was applied to activate the catalysts. As references, commercially available cubic and tetragonal barium titanates were used, with the addition of benchmark P25 TiO2 in some cases. Increasing the calcination temperature resulted in increased primary crystallite sizes, decreased specific surface areas, and slightly redshifted band gaps. On the one hand, the overall photooxidation activity of the samples for pollutant degradation was rather low, possibly due to their unfavorable valence band maximum position. On the other hand, our samples displayed significantly superior photoreduction activity, surpassing that of all the references, including P25 TiO2. The high photoactivity was mainly attributed to the specific surface areas that changed per the efficiency of the samples. Last, the cost comparison calculations showed that applying our calcination technique is 29.5% more cost-efficient than conventional calcination, and the same amount of energy is sufficient for preparing even a 1.4 times higher amount of barium titanite.

A robust floating oxygen-doped graphitic carbon nitride sheet for efficient photocatalytic CO2 conversion

Photocatalytic CO2 reduction offers a promising approach for converting CO2 into valuable chemicals. However, typical conversion systems suffer from inefficient CO2 mass transfer and complex recycling processes. In this study, we developed a floating sheet as a robust photocatalytic CO2 conversion system by integrating graphitic carbon nitride (CN) nanosheets onto polytetrafluoroethylene (PTFE) fiber membrane, followed by oxygen (O) doping into the CN (CN-O) via oxygen-plasma treatment. The floatable CN-O/PTFE sheet exhibits slight wettability in water under 0.25 MPa of CO2 pressure in our reactor system, facilitating the delivery of dissolved CO2 to the CN-O photocatalyst surface. O-doping enhances the visible light absorption and improves the separation and transport efficiency of photogenerated electrons and holes due to O-doping-induced states in CN. Consequently, the floating CN-O/PTFE system achieves an exceptional photocatalytic CO2 conversion rate of 102.3 μmol g-1h-1, approximately 4.8 times higher than a conventional CN-powder dispersion system in water. Moreover, the sheet demonstrates excellent cycling durability, with no significant exfoliation of the catalytic layer or reduction in CO2 photoreduction activity after 20 consecutive cycles. This study presents a novel approach to designing photocatalytic systems for efficient CO2 conversion.

Synergistic effects of carbon coating and Bi-bridge in S-scheme C@CuO/Bi/Bi2MoO6 nanocomposites for enhanced photoreduction of Cr(VI)

The S-scheme mechanism in photocatalysis offers a promising approach to significantly enhance photoreductive activity. Here, using Bi dots as electronic media, and by changing the amount of added C@CuO on the surface of flower-shaped Bi2MoO6, a diverse range of CBM-x heterojunctions, were synthesized using a multi-step approach that incorporated solvothermal preparation and calcination methods. CBM-10 exhibited excellent photocatalytic activity: 96.9 % of Cr(VI) removal in 30 min, which was 38.0-fold better than CuO, 4.2-fold higher than pristine Bi2MoO6. Furthermore, even after five cycles of use, CBM-10 showed outstanding stability. Experiments to capture the active species revealed that electrons play a crucial role in the photocatalytic reduction of Cr(VI). In these heterojunctions, carbon doping leads to the formation of coatings on the semiconductor materials to promote the migration and separation of photogenerated carriers. The presence of carbon coating is beneficial to improve the stability of CBM-10. Bi dots grown on Bi2MoO6 nanosheets can act as electron transport channels in C@CuO/Bi/Bi2MoO6, accelerate photoinduced carrier separation. The internal electric field, and the existence of “S-scheme” charge transfer mechanism was verified by the combination of atomic force microscope and synchronous illumination X-ray photoelectron spectroscopy. This process significantly mitigates the recombination of photo-induced carriers, enhancing the overall photoreduction efficacy. This study presents a novel method for developing S-scheme heterojunction to enhance the effectiveness of Cr(VI) decontamination, paves a promising route to heavy metal removal by mild photo-reductive system, and provides new insights into the design of photocatalysts with enhanced redox capabilities.

Ag–Pt Alloy Nanoparticles Modified Zn‐Based Nanosheets for Highly Selective CO2 Photoreduction to CH4

AbstractMulti‐electron involved photoreduction of CO2 to hydrocarbon fuels is a long‐standing challenge, particularly in manipulating the selectivity of the target products. Here, a novel Ag–Pt bimetallic alloy on Zn‐based supports by photo‐deposition is designed for photocatalytic CO2 reduction to CH4 without any additives. This photocatalyst exhibits ≈ 98.9% selectivity for CH4. Experimental and theoretical calculations demonstrated that the excellent performance of the photocatalyst can be attributed to the localized surface plasmon resonance effect of metals, as well as the synergistic effects of the bimetallic sites. These factors are found to be beneficial not only for capturing solar radiation and facilitating electron migration but also for promoting the adsorption and activation of CO2 and the protonation of *CO. As a result, the photocatalyst achieved high selectivity and activity of photoreduction of CO2 to CH4. This work provides insights into the design of photocatalysts with highly selective target products for CO2 reduction.

Crystal plane engineering-tailored Co-Ni bimetallic sites in CoNiO2 to achieve efficient photocatalytic CO2 reduction

Aligning the atomic structure of catalyst by the crystal-plane engineering is an effective strategy to enhance the photocatalytic activity. In this paper, the CoNiO2 nanosheets (NSs) with (200) and nanorods (NRs) with (111) crystal planes were successfully prepared through a simple hydrothermal method for CO2 photoreduction. The experimental results indicated that the CNO NRs had excellent CO2 photoreduction performance. The CO and CH4 yields over CNO NRs were about 48.66 and 5.84 μmol·g−1·h−1, which were about 2.62 and 2.61 times stronger than that of CNO NSs. Moreover, it was also about 10.70 and 6.25 times as good as the TiO2 commercial powder, respectively. Experimental and theoretical calculations demonstrated that the Co-Ni bimetallic sites on the (111) crystal plane of CNO NRs can effectively enhance the CO2 adsorption and activation ability compared with the single Ni site on the (200) crystal plane of CNO NSs. Besides, the energy barrier required for the development of the critical intermediate *COOH from *CO2 was greatly reduced on the Co-Ni bimetallic sites, thereby improving the CO2 photoreduction activity. The reaction paths were inferred by in-situ FTIR and 13C isotope tracer techniques, and finally a potential enhancement mechanism of the crystal plane engineering induces bimetallic sites to promote CO2 adsorption and activation process has been proposed.

CdWO4 Sub‐1 nm Nanowires for Visible‐light CO2 Photoreduction

Quantum size effect usually causes energy level splitting and band broadening as material size decreases. However, this may change again by the surface adsorbents, doping and defects, which rarely attracts much attention. Herein, CdWO4 sub‐1 nm nanowires (SNWs) with oleylamine adsorption, PO43‐‐doping and oxygen defects are synthesized by combining Cd(CH3COO)2, H3PW12O40 (PW12) and oleylamine (abbreviated as PO43‐‐CdWO4‐X SNWs). Compared with bulk CdWO4, they exhibit unexpected absorption spectra (extended from 292 nm to 453 nm) and bandgap (reduced from 4.25 eV to 2.74 eV), thus bringing remarkable visible‐light CO2 photoreduction activity. Under 410 nm LED light irradiation, PO43‐‐CdWO4‐40 SNWs exhibit the highest photocatalytic performance with a CO2‐to‐CO generation rate of 1685 µmol g‐1 h‐1. Density functional theory (DFT) calculations demonstrate the adsorbed oleylamine raises the valence band and enhances the adsorption of reaction substrate and intermediates, thus decreasing their reduction energy barriers. Furthermore, PO43‐‐doping and oxygen defects will generate defect energy band below the conduction band of PO43‐‐CdWO4‐40 SNWs, resulting in remarkable visible light absorption and superior photocatalytic CO2 reduction performance. This work highlights the significant impacts of surface adsorbents, doping and defects on the physicochemical and catalytic properties of sub‐nano materials.

CdWO4 Sub-1 nm Nanowires for Visible-Light CO2 Photoreduction.

Quantum size effect usually causes energy level splitting and band broadening as material size decreases. However, this may change again by the surface adsorbents, doping and defects, which rarely attracts much attention. Herein, CdWO4 sub-1 nm nanowires (SNWs) with oleylamine adsorption, PO4 3--doping and oxygen defects are synthesized by combining Cd(CH3COO)2, H3PW12O40 (PW12) and oleylamine (abbreviated as PO4 3--CdWO4-X SNWs). Compared with bulk CdWO4, they exhibit unexpected absorption spectra (extended from 292 nm to 453 nm) and band gap (reduced from 4.25 eV to 2.74 eV), thus bringing remarkable visible-light CO2 photoreduction activity. Under 410 nm LED light irradiation, PO4 3--CdWO4-40 SNWs exhibit the highest photocatalytic performance with a CO2-to-CO generation rate of 1685 μmol g-1 h-1. Density functional theory (DFT) calculations demonstrate the adsorbed oleylamine raises the valence band and enhances the adsorption of reaction substrate and intermediates, thus decreasing their reduction energy barriers. Furthermore, PO4 3--doping and oxygen defects will generate defect energy band below the conduction band of PO4 3--CdWO4-40 SNWs, resulting in remarkable visible light absorption and superior photocatalytic CO2 reduction performance. This work highlights the significant impacts of surface adsorbents, doping and defects on the physicochemical and catalytic properties of sub-nano materials.

Sponge-shaped Au nanoparticles: a stand-alone metallic photocatalyst for driving the light-induced CO2 reduction reaction

Coinage metal nanoparticles (NPs) enable plasmonic catalysis by generating hot carriers that drive chemical reactions. Making NPs porous enhances the adsorption of reactant molecules. We present a dewetting and dealloying strategy to fabricate porous gold nanoparticles (Au-Sponge) and compare their CO2 photoreduction activity with respect to the conventional gold nanoisland (Au-Island) morphology. Porous gold nanoparticles exhibit an unusually broad and red-shifted plasmon resonance which is in agreement with the results of finite difference time domain (FDTD) simulations. The key insight of this work is that the multi-step reduction of CO2 driven by short-lived hot carriers generated by the d → s interband transition proceeds extremely quickly as evidenced by the generation of methane. A 3.8-fold enhancement in the photocatalytic performance is observed for the Au-Sponge in comparison to the Au-Island. Electrochemical cyclic voltammetry measurements confirm the 2.5-fold increase in the surface area and roughness factor of the Au-Sponge sample due to its porous nature. Our results indicate that the product yield is limited by the amount of surface adsorbates i.e. reactant-limited. Isotope-labeled mass spectrometry using 13CO2 was used to confirm that the reaction product (13CH4) originated from CO2 photoreduction. We present the plasmon-mediated photocatalytic transformation of 4-aminothiophenol (PATP) into p,p'-dimercaptoazobenzene (DMAB) using Au-Sponge and Au-Island samples.

Facilitating photocatalytic CO2 methanation via synergetic feed of photon-induced carriers and reactants over S-scheme BiVO4@TiO2 nanograss/needle arrays

Herein, a unique structure BiVO4@TiO2 nanograss/needle arrays S-scheme heterojunction photocatalyst for CO2 photoreduction reaction was created. The photocatalyst can drive electrons to the reactive spots spontaneously and continuously, which effectively tackles the problem of severe recombination and disordered migration of photogenerated carriers. Theoretical calculations and experimental results demonstrate that adding BMIM-BF4 ionic liquid to generate BMIM-*CO2 intermediate promotes CO2 activation and enrichment of reactants concentration around the catalytic sites. Benefiting from the sufficient electron supply of catalytic sites and reinforced reactants supply in the interfacial microenvironment, the BiVO4@TiO2 photocatalyst shows high selectivity and activity of CO2-to-CH4 conversion. The CH4 selectivity increased to 57.3 % (132.7 μmol m-2h−1) and the methanation activity was increased by 8.6 times in the 5.0 % BMIM-BF4 aqueous solution. Significantly, the BiVO4@TiO2 NNAs catalyst obtains a solar-to-fuels energy efficiency of ∼ 0.46 ‰ under ultraviolet-enhanced light sources without any sacrificial agent or co-catalyst. This work displays the relationship between reaction process factors (electron supply, CO2 molecule, and proton supply) and CO2 photoreduction activity and selectivity, giving new insight into achieving efficient CO2 photoreduction conversion.

Effects of MOF-MoO3-x derivatives synthesis and oxygen defect engineering on photocatalytic CO2 reduction

Photocatalytic conversion of CO2 into valuable fuels is considered a promising approach for the development of sustainable and renewable energy sources. In this study, we utilized Mo-MOF as a precursor to obtain MoO3 by pyrolytic derivatization and treated it to obtain MOF-MoO3-x containing oxygen vacancies as a catalyst for the photocatalytic reduction of CO2 to CO. MOF derivatization altered the morphology of the MoO3, which made the formation of oxygen vacancies easier and facilitated the separation of electron-hole pairs. Meanwhile, the increased specific surface area and the appearance of surface oxygen vacancies enhanced the CO2 adsorption and activation capabilities of MOF-MoO3-x. As a result, MOF-MoO3-x demonstrated a significant enhances in the photoreduction activity of CO2. Its CO yield was 29.1 μmolg−1h−1, which was 3.7 times higher than that of MOF-MoO3 and 2.4 times higher than that of H-MoO3-x. This innovative strategy may provide a new avenue for improving the comprehensive performance of photocatalysts and developing renewable energy sources.

Regulation of charge transfer direction and key steps via Y modification of redox-active sites on borocarbonitride for photocatalytic CO2 reduction

Hexagonal borocarbonitride (h-BCN) have garnered significant attention for their unique optoelectronic properties in solar-to-fuel conversions. However, the efficiency of h-BCN in the field of photocatalytic CO2 reduction is limited by high reaction energy barriers and serious charge recombination. Here, a Y-modified h-BCN were synthesized through an organic-inorganic hybrid precursor pyrolysis method. Both theoretical simulation and experimental analysis demonstrated that the Y-modified sample exhibits an inhomogeneous charge distribution that favours rapid charge transfer and can decrease the reaction barrier of the rate-control step. Further investigations indicated that adding Y changes the electronic structure of BCN, which leads to rapid charge transfer/separation and an increased lifespan for photoinduced electrons. As a result, 2.5%Y/BCN exhibited improved CO2 photoreduction activity with a fuel yield of 50.35 μmol g−1. Notably, this outstanding performance was achieved without the use of any cocatalyst or sacrificial agent. In the meanwhile, cycle test shows the photocatalyst's great stability. The findings provide a useful suggestions for BCN-based photocatalysts.

Near-infrared-responsive sea-urchin-like Ag6Si2O7/Bi19Br3S27 S-scheme heterojunction for efficient CO2 photoreduction

The construction of S-scheme heterojunctions effectively facilitates the spatial separation of photogenerated charge carriers for their involvement in photoreactions. However, the inefficient utilization of solar energy in these heterostructures is often due to unfavorable band-edge positions and suboptimal charge transport dynamics, which result in low photocatalytic efficiency when considering kinetic factors. In this study, sea urchin–like Bi19Br3S27/Ag6Si2O7 S-scheme heterojunctions are fabricated, which exhibit excellent CO2 photoreduction performance under ultraviolet, visible, and near-infrared (NIR) light illumination. Experimental data and density functional theory calculations confirm the S-scheme charge transfer mechanisms, which enable the efficient separation of photogenerated carriers for CO2 reduction. Consequently, the optimized Ag6Si2O7/Bi19Br3S27 heterostructures exhibit superior CO2 photoreduction activity under NIR light irradiation. This approach offers a strategy for designing advanced NIR-light-responsive photocatalysts for efficient CO2 photoreduction.

Theoretical Study on Photocatalytic Reduction of CO2 on Anatase/Rutile Mixed-Phase TiO2.

The construction of anatase/rutile heterojunctions in TiO2 is an effective way of improving the CO2 photoreduction activity. Yet, the origin of the superior photocatalytic performance is still unclear. To solve this issue, the band edges between anatase and rutile phases were theoretically determined based on the three-phase atomic model of (112)A/II/(101)R, and simultaneously the CO2 reduction processes were meticulously investigated. Our calculations show that photogenerated holes can move readily from anatase to rutile via the thin intermediated II phase, while photoelectrons flowing in the opposite direction may be impeded due to the electron trapping sites at the II phase. However, the large potential drop across the anatase/rutile interface and the strong built-in electric field can provide an effective driving force for photoelectrons' migration to anatase. In addition, the II phase can better enhance the solar light utilization of (112)A/(100)II, including a wide light response range and an intensive optical absorption coefficient. Meanwhile, the mixed-phase TiO2 possesses negligible hydrogenation energy (CO2 to COOH*) and lower rate-limiting energy (HCOOH* to HCO*), which greatly facilitate CH3OH generation. The efficient charge separation, strengthened light absorption, and facile CO2 reduction successfully demonstrate that the anatase/rutile mixed-phase TiO2 is an efficient photocatalyst utilized for CO2 conversion.

Amphiphilic heterojunctions with atomically dispersed copper–alkynyl active units for highly efficient CO2 photoreduction

The efficiency of CO2 photoreduction is limited by slow charge kinetics and the mass transfer of hydrophobic CO2 and H2O over the photocatalyst. Herein, we present a copper–alkynyl bond coordination polymer (CA-CP) with atomically-dispersed copper–alkynyl units (ADCAUs). By incorporating hydrophobic CA-CP with hydrophilic iodine vacancy-rich bismuth oxyhalides (IV-BX), we construct amphiphilic heterojunction photocatalysts (CA-CP/IV-BX) for visible-light-driven CO2 photoreduction. CA-CP/IV-BX achieves excellent stability, 100 % CO selectivity and a CO-evolution rate of 157.6 μmol g−1 h−1 coupled with O2 releasing. Experimental and theoretical calculations elucidate that the ADCAUs favor adsorption and activation of CO2, and have high CO selectivity. Moreover, the amphiphilic janus structure not only ensures the spatial synergy effect of CO2 reduction and H2O oxidation, but also promotes charge separation and proton feeding, boosting CO2 photoreduction activity. This work develops Cu–alkynyl coordination polymer photocatalysts with ADCAUs and provides insights into hydrophobic–hydrophilic biphasic photocatalysts for synergistic CO2 reduction and H2O oxidation.

An Ester-Functionalized Bidentate Titanium-based Metal-Organic Framework with Visible-Light Enhanced Activity for CO2 Photoreduction.

The limited visible light response is a critical drawback that hampers the photocatalytic efficacy of Ti-MOFs. However, study concerning the enhancement of the visible-light response of Ti-MOFs is still in its nascent stage. In this study, we employ the 'dual-ligand decrystallization strategy' to manipulate the electronic environment of Ti4+, leading to the synthesis of three ester-functionalized bidentate Ti-MOFs with enhanced visible light response. Our findings reveal that this approach not only reduces the bandgap of Ti-MOFs but also enhances their photocatalytic activity for carbon dioxide reduction. Specifically, compared to the bandgap of Ti-BPDC at 2.98 eV, the bandgap of Ti-BPDC-CA 1 : 2 has been reduced to 2.14 eV. Moreover, Ti-BPDC-CA 1 : 2 exhibits extraordinary photocatalytic activity with the formic acid (HCOOH) production rate of 617 μmol g-1 h-1 with over 99.5 % selectivity, which is 3.47 times higher than that of Ti-BPDC. Besides providing a cost-effective strategy for enhancing the visible light response of Ti-MOFs, our study also serves as an illustrative example for establishing the correlation between electronic structure and optical properties.

Wavelength-selective, time-resolved, and visible-light-responsive multicolor switching systems for multistate dynamic information encryption

Visible-light-responsive photoreversible multi-color switching systems (PMCSSs) are attractive to meet the advanced demands in dynamic information encryption. Particularly, PMCSSs with wavelength-selective and time-resolved color switching are highly important but underexplored. Here, a new strategy is proposed to realize wavelength-selective, time-resolved, and visible-light-responsive PMCSSs by integrating acetamide ligand-capping CdS (CdS-NH2) nanoparticles and various redox dyes in solid films for multistate dynamic information encryption. The –NH2 groups of surface-bounded CH3CONH2 act as sacrificial electron donors for scavenging photogenerated holes to endow the CdS-NH2 nanoparticles high photoreductive ability and activity in a broad visible light range from 400 to 515 nm, thus enabling the long-waited wavelength-selective multicolor switching via coupling the wavelength-dependent photoreductivity of CdS-NH2 nanoparticles and the discoloration kinetics of redox dyes, such as methylene blue (MB) and phenosafranine (PS). Moreover, the time-dependent color switching during recoloration process of the color switching system can be modulated by tuning the oxidation kinetics of MB and methylene green (MG), enabling time-resolved dynamic imaging characteristics. Based on the unusual properties of the PMCSSs, a kind of wavelength-selective and time-resolved codes are designed for advanced dynamic information encryption. This work provides new guidance for developing of new PMCSSs for information encryption with high security requirements.

Twist angle-driven photoreduction of carbon dioxide on bilayer black phosphorus – A first-principles study

Utilizing first principles calculations, the product selectivity in photocatalytic CO2 reduction was modulated by manipulating the twisted angle in bilayer black phosphorus. Four twisted angles, 0° (AA stacking), 15.40°, 19.00° and 24.66°, were constructed. Comprehensive investigations revealed enhanced carrier mobility and lifetime, especially at a 24.66° twist. Furthermore, an in-depth analysis of the CO2 reduction processes in these four systems was undertaken. Our simulations indicate that in the AA stacking, the photocatalytic CO2 reduction yields multiple products, including HCHO, CH3OH, and CH4, demonstrating limited product selectivity. However, when the surface is twisted at 15.40°, 19.00°, or 24.66°, the sole product is CH4. Remarkably, the 24.66° configuration exhibits the lowest energy barrier for the rate-determining step, measuring just 1.29 eV. These observations suggest that by carefully adjusting the twisted angle in bilayer black phosphorus, we can significantly improve both the activity and selectivity of CO2 photoreduction.