Highly Stable Perovskite Oxides for Electrocatalytic Acidic NOx- Reduction Streamlining Ammonia Synthesis from Air.

Electrochemical nitrogen oxide ions reduction reaction (NOx-RR) shows great opportunity for ammonia production under ambient conditions. Yet, performing NOx-RR in strong acidic conditions remains challenging due to the corrosion effect on the catalyst and competing hydrogen evolution reactions. Here, we demonstrate a stable La1.5Sr0.5Ni0.5Fe0.5O4 perovskite oxide for the NOx-RR at pH 0, achieving a Faradaic efficiency for ammonia of approaching 100% at a current density of 2 A cm-2 in a H-type cell. At industrially relevant current density, the NOx-RR system shows stable cell voltage and Faradaic efficiency for >350 h in membrane electrode assembly (MEA) at pH 0. By integrating the catalyst in a stacked MEA with a series connection, we have successfully obtained a record-breaking 2.578 g h-1 NH3 production rate at 20 A. This catalyst's unique acid-operability streamlines downstream ammonia utilization for direct ammonium salt production and upstream integration with NOx sources. Techno-economic and lifecycle assessments reveal substantial economic advantages for this ammonia production strategy, even when coupled with a plasma-based NOx production system, presenting a sustainable complement to the conventional Haber-Bosch process.

Spin-Steered Photosynthesis of H2O2 in Magnetic Single-Atom Modified Covalent Triazine Frameworks: A Density Functional Theory Study.

Covalent Organic Frameworks (COFs) demonstrate promising potential in the photocatalytic synthesis of H2O2 owing to favorable light absorption, superior charge separation, and considerable surface area. However, the efficiency of H2O2 photosynthesis is impeded by insufficient O2 adsorption sites and a high reaction barrier. In this work, various metal single atoms (Fe, Co, Ni) are introduced onto covalent triazine frameworks (CTFs) with N-N coordination sites to significantly enhance O2 adsorption and optimize H2O2 synthesis. Computational findings suggest that the presence of Fe, Co, and Ni not only enhances O2 adsorption but also exerts an influence on the reaction pathway of H2O2. Significantly, Fe exhibits a distinct advantage in modulating O2 adsorption through its unique electron spin state when compared to Co and Ni, as confirmed by crystal orbital Hamilton population (COHP) analysis. Additionally, this integration of metal atoms also improves light absorption and charge separation in CTFs. The study provides strategic insight into elevating H2O2 production by incorporating tailored metal single atoms into COFs.

Complete Photooxidation of Formaldehyde to CO2 via Ni-Dual-Atom Decorated Crystalline Triazine Frameworks: A DFT Study.

Formaldehyde (CH2O) emerges as a significant air pollutant, necessitating effective strategies for its oxidation to mitigate adverse impacts on human health and the environment. Among various technologies, the photooxidation of CH2O stands out owing to its affordability, safety, and effectiveness. Nitrogen-rich crystalline triazine-based organic frameworks (CTFs) exhibit considerable potential in this domain. Nevertheless, the weak and unstable CH2O adsorption hinders the overall oxidation efficiency of CTF. To address this limitation, we incorporate single and dual Ni atoms into nitrogen-rich CTFs by density functional theory (DFT) calculations, resulting in CTF-Ni and CTF-2Ni. This strategic modification significantly enhances the adsorption capability of CH2O. Notably, this synergy between Ni dual atoms activates CH2O by strong chemical adsorption, thereby reducing the energy barrier of CH2O oxidation and achieving the complete oxidation of CH2O to CO2. Moreover, the introduction of dual-atom Ni over CTF ameliorates visible and near-infrared light absorption and facilitates photoexcited charge transfer and separation. Finally, the underlying mechanisms of complete CH2O oxidation over CTF-2Ni are proposed. This work offers novel insights into the rational design of photocatalysts for CH2O oxidation through the integration of Ni dual atoms into CTFs.

Metal Sulfide S-Scheme Homojunction for Photocatalytic Selective Phenylcarbinol Oxidation.

Metal sulfide-based homojunction photocatalysts are extensively explored with improved photocatalytic performance. However, the construction of metal sulfide-based S-scheme homojunction remains a challenge. Herein, the fabrication of 2D CdIn2S4 nanosheets coated 3D CdIn2S4 octahedra (referred to as 2D/3D n-CIS/o-CIS) S-scheme homojunction photocatalyst is reported by simply adjustment of polyvinyl pyrrolidone amount during the solvothermal synthesis. The formation of S-scheme homojunction within n-CIS/o-CIS is systematically investigated via a series of characterizations, which can generate an internal electric field to facilitate the separation and migration of photogenerated electron-hole pairs. The 2D/3D n-CIS/o-CIS composite exhibits significantly improved photocatalytic activity and stability in the selective oxidation of phenylcarbinol (PhCH2OH) to benzaldehyde (PhCHO) when compared to pure n-CIS and o-CIS samples under visible light irradiation. It is hoped that this work can contribute novel insights into the development of metal sulfides S-scheme homojunction photocatalysts for solar energy conversion.

Tunable Impedance of Cobalt Loaded Carbon for Wide-Range Electromagnetic Wave Absorption.

Impedance matching modulation of the electromagnetic wave (EMW) absorbers toward broad effective absorption bandwidth (EAB) is the ultimate aim in EMW attenuation applications. Here, a Joule heating strategy is reported for preparation of the Co-loaded carbon (Co/C) absorber with tunable impedance characteristics. Typically, the size of the Co can be regulated to range from single-atoms to clusters, and to nanocrystals. The varied sizes of the Co combined with different graphitization degrees of carbon can result in different relative input impedances and electromagnetic loss, leading to the tunable EMW absorption properties of the Co/C absorber. By meticulously coalescing the different prepared Co/C, the working frequency can be easily tuned, covering Ku, X, and C bands. Furthermore, the Co/C demonstrates a high EMW attenuation due to its unique dielectric loss capability and magnetic loss characteristics. The abundant interfaces of Co/C can also contribute to the enhanced interfacial polarization for improving EMW attenuation. This work demonstrates the importance of optimizing the metal and carbon interaction to the impedance matching toward wide EAB of the EMW absorbers.

The Mars-Van Krevelen cycle and non-noble metal Ni jointly promoting Z-scheme charge transfer: a study on the photothermal synergy effect applied in selectively oxidizing aromatic alcohols.

Photothermal catalysis is a promising method for selectively oxidizing organic compounds, effectively addressing the energy-intensive and low-selective processes of thermal catalysis, as well as the slow reaction rates of photocatalysis. In this study, a ternary photothermal catalyst, Ni/CeO2/CdS, was synthesized using a simple calcination and solvothermal method. The catalyst demonstrated remarkable improvement in reaction rates and achieved nearly 100% selectivity in converting benzyl alcohol to benzaldehyde through photothermal catalysis at normal pressure. The reaction rates were 5.9 times and 63 times higher than those of CdS and Ni/CeO2 individually. XPS analysis confirmed that the thermal catalysis followed the Mars-Van Krevelen (MVK) mechanism and also proved that photocatalysis facilitated the MVK cycle. Additionally, DFT calculations showed that Ni acted as an electron transfer channel, facilitating efficient Z-scheme charge transfer. The in situ infrared technique was used to dynamically monitor the reaction process and explain the high selectivity of the product. Furthermore, detailed explanations of photocatalysis, thermocatalysis, and photothermal synergistic catalysis were proposed based on the aforementioned characterization and theoretical calculations. This approach establishes a theoretical foundation for the development of efficient photothermal catalysts.

Photoredox Coupling of CO2 Reduction with Benzyl Alcohol Oxidation over Ternary Metal Chalcogenides (ZnmIn2S3+m, m = 1-5) with Regulable Products Selectivity.

Integrating photocatalytic CO2 reduction with selective benzyl alcohol (BA) oxidation in one photoredox reaction system is a promising way for the simultaneous utilization of photogenerated electrons and holes. Herein, ZnmIn2S3+m (m = 1-5) semiconductors (ZnIn2S4, Zn2In2S5, Zn3In2S6, Zn4In2S7, and Zn5In2S8) with various composition faults were synthesized via a simple hydrothermal method and used for effective selective dehydrocoupling of benzyl alcohol into high-value C-C coupling products and reduction of CO2 into syngas under visible light. The absorption edge of ZnmIn2S3+m samples shifted to shorter wavelengths as the atomic ratio of Zn/In was increased. The conduction band and valence band position can be adjusted by changing the Zn/In ratio, resulting in controllable photoredox ability for selective BA oxidation and CO2 reduction. For example, the selectivity of benzaldehyde (BAD) product was reduced from 76% (ZnIn2S4, ZIS1) to 27% (Zn4In2S7, ZIS4), while the selectivity of hydrobenzoin (HB) was increased from 22% to 56%. Additionally, the H2 formation rate on ZIS1 (1.6 mmol/g/h) was 1.6 times higher than that of ZIS4 (1.0 mmol/g/h), and the CO formation rate on ZIS4 (0.32 mmol/g/h) was three times higher than that of ZIS1 (0.13 mmol/g/h), demonstrating that syngas with different H2/CO ratios can be obtained by controlling the Zn/In ratio in ZnmIn2S3+m. This study provides new insights into unveiling the relationship of structure-property of ZnmIn2S3+m layered crystals, which are valuable for implementation in a wide range of environment and energy applications.

Tunable Interfacial Charge Transfer in a 2D-2D Composite for Efficient Visible-Light-Driven CO2 Conversion.

Photocatalytic CO2 conversion for hydrocarbon fuel production has been known as one of the most promising strategies for achieving carbon neutrality. Yet, its conversion efficiency remains unsatisfactory mainly due to its severe charge-transfer resistance and slow charge kinetics. Herein, a tunable interfacial charge transfer on an oxygen-vacancies-modified bismuth molybdate nanoflower assembled by 2D nanosheets (BMOVs) and 2D bismuthene composite (Bi/BMOVs) is demonstrated for photocatalytic CO2 conversion. Specifically, the meticulous design of the Ohmic contact formed between BMOVs and bismuthene can allow the modulation of the interfacial charge-transfer resistance. According to density functional theory (DFT) simulations, it is ascertained that such exceptional charge kinetics is attributed to the tunable built-in electric field (IEF) of the Ohmic contact. As such, the photocatalytic CO2 reduction performance of the optimized Bi/BMOVs (CO and CH4 productions rate of 169.93 and 4.65 µmol g-1 h-1 , respectively) is ca. 10 times higher than that of the pristine BMO (CO and CH4 production rates of 16.06 and 0.51 µmol g-1 h-1 , respectively). The tunable interfacial resistance of the Ohmic contact reported in this work can shed some important light on the design of highly efficient photocatalysts for both energy and environmental applications.

Interfacial C-S Bonds of g-C3 N4 /Bi19 Br3 S27 S-Scheme Heterojunction for Enhanced Photocatalytic CO2 Reduction.

Step-scheme (S-scheme) heterojunctions have been extensively studied in photocatalytic carbon dioxide (CO2 ) reduction due to their excellent charge separation and high redox ability. The built-in electric field at the interface of a S-scheme heterojunction serves as the driving force for charge transfer, however, the poor interfacial contact greatly restricts the carrier migration rate. Herein, we synthesized the g-C3 N4 /Bi19 Br3 S27 S-scheme heterostructure through in situ deposition of Bi19 Br3 S27 (BBS) on porous g-C3 N4 (P-CN) nanosheets. The C-S bonds formed at the interface help to enhance the built-in electric field, thereby promoting the charge transfer and separation. As a result, the CO2 reduction reaction performance of 10 %Bi19 Br3 S27 /g-C3 N4 (BBS/P-CN) reaches 32.78 µmol g-1 h-1 , which is 341.4 and 18.7 times higher than that of pure BBS and P-CN, respectively. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) prove the presence of chemical bonds (C-S) between the P-CN and BBS. The S-scheme charge-transfer mechanism was analyzed via XPS and density functional theory (DFT) calculations. This work provides a new idea for designing heterojunction photocatalysts with interfacial chemical bonds to achieve high charge-transfer and catalytic activity.

Surface-active site modulation of the S-scheme heterojunction toward exceptional photocatalytic performance.

Heterojunction photocatalysts have shown their immense capability in enhancing photogenerated charge carrier separation. Yet, the intrinsic scarcity of active sites in semiconductor components of heterojunction photocatalysts limits their potential for photocatalysis being used in practical applications. Herein, we employ a non-noble metal cocatalyst (i.e., NiS) for modulating a S-scheme heterojunction photocatalyst consisting of Cd3(C3N3S3)2 (CdCNS) and CdS. It is revealed that the formation of the CdCNS/CdS S-scheme heterojunction can enable optimal photogenerated charge carrier utilization efficiency and optimized redox capability. More importantly, the meticulous loading of NiS can play multiple roles in enhancing the photocatalytic performance of the CdCNS/CdS photocatalyst, including endowing it with abundant surface-active sites and acting as a photogenerated electron acceptor. As a result, the optimized NiS-loaded CdCNS/CdS attains an excellent hydrogen production rate of 38.17 mmol g-1 h-1, to reach a quantum efficiency of 29.02% at 420 nm. The results reported in this work provide an interesting insight into the important roles of surface-active site modulation in optimizing photocatalytic performances.

Cooperative Coupling of H2 O2 Production and Organic Synthesis over a Floatable Polystyrene-Sphere-Supported TiO2 /Bi2 O3 S-Scheme Photocatalyst.

Cooperative coupling of photocatalytic H2 O2 production with organic synthesis has an expansive perspective in converting solar energy into storable chemical energy. However, traditional powder photocatalysts suffer from severe agglomeration, limited light absorption, poor gas reactant accessibility, and reusable difficulty, which greatly hinders their large-scale application. Herein, floatable composite photocatalysts are synthesized by immobilizing hydrophobic TiO2 and Bi2 O3 on lightweight polystyrene (PS) spheres via hydrothermal and photodeposition methods. The floatable photocatalysts are not only solar transparent, but also upgrade the contact between reactants and photocatalysts. Thus, the floatable step-scheme (S-scheme) TiO2 /Bi2 O3 photocatalyst exhibits a drastically enhanced H2 O2 yield of 1.15 mm h-1 and decent furfuryl alcohol conversion to furoic acid synchronously. Furthermore, the S-scheme mechanism and dynamics are systematically investigated by in situ irradiated X-ray photoelectron spectroscopy and femtosecond transient absorption spectrum analyses. In situ Fourier transform infrared spectroscopy and density functional theory calculations reveal the mechanism of furoic acid evolution. The ingenious design of floatable photocatalysts not only furnishes insight into maximizing photocatalytic reaction kinetics but also provides a new route for highly efficient heterogeneous catalysis.

Photocatalytic H2 Evolution Coupled with Furfuralcohol Oxidation over Pt-Modified ZnCdS Solid Solution.

Coupling photocatalytic H2 production with organic synthesis attracts immense interest in the energy and chemical engineering field for the low-cost, clean, and sustainable generation of green energy and value-added products. Nevertheless, the performance of current photocatalysts is greatly limited by grievous charge recombination and tardy H2 evolution. To tackle these issues, a Pt nanocluster-modified ZnCdS solid solution is fabricated for photocatalytic H2 production and selective furfuralcohol oxidation. The internal electric field inside the ZnCdS and Schottky junction between ZnCdS and Pt nanoclusters drastically ameliorate charge separation. Meanwhile, the Pt nanoclusters remarkably expedite the H2 evolution kinetics on ZnCdS. As a result, the H2 production rate over Pt-loaded ZnCdS reaches 1045 µmol g-1 h-1 , which is about 26- and 70-fold that of CdS and ZnS, respectively. Under light irradiation for 3 h, the conversion of furfuralcohol to furfural reaches 71% with 89% furfural selectivity. The photocatalytic mechanism is investigated by in situ characterizations and theoretical calculations.

Efficient interfacial charge transfer of 2D/2D porous carbon nitride/bismuth oxychloride step-scheme heterojunction for boosted solar-driven CO2 reduction.

Heterostructured photocatalysts are promising candidates in the photocatalysis field, and the heterojunction plays a vital role in the separation of spatial charge carriers. Here, a heterojunction was fabricated by the in situ growth of ultrathin Bi12O17Cl2 (BOC) nanosheets (NSs) onto porous g-C3N4 (PGCN) NSs. The NSs' nanostructure can effectively shorten the diffusion path of charge carriers and thus promote interfacial charge migration, which can improve the surface photocatalytic activity. The X-ray photoelectron spectroscopy spectra and the experimental measured Fermi level (EF) indicate that electrons transfer from PGCN to BOC, which leads to the formation of the built-in electric field with the orientation from PGCN to BOC. Driven by the built-in electric field, the charge carriers transfer through a step-like pathway. This step-scheme porous g-C3N4/Bi12O17Cl2 (PGCN/BOC) heterostructured nanocomposite displays an enhanced photocatalytic performance compared with pure BOC and PGCN. This work provides new insight into the novel construction of a step-scheme heterojunction toward photocatalytic CO2 reduction.

Construction of organic-inorganic cadmium sulfide/diethylenetriamine hybrids for efficient photocatalytic hydrogen production.

The design and control of effective, sustainable, cheap, and reusable photocatalysts are crucial to the development of solar energy conversion to hydrogen (H2) for solving environmental problems. The cadmium sulfide/diethylenetriamine (CdS/DETA) hybrid in a single crystalline structure was achieved by a solvothermal approach. The organic-inorganic CdS/DETA hybrid shows high performance and satisfactory stability for H2 production under visible-light irradiation. The synergetic chemical coupling effect between CdS and DETA leads to a marked increase in the H2 generation rate and the apparent quantum yield. H2-production rate of CdS/DETA24 under visible light illumination are 31.7% and 8059.5µmolg-1h-1, respectively, which is 3.5 times more than CdS nanorods without DETA. Our findings may give a promising method to improve CdS for efficient electron-hole separation, electron transferring and anticorrosion in photocatalytic process, which reforms the conventional organic-inorganic hybrid system.

Controllable synthesis of inorganic-organic Zn1-xCdxS-DETA solid solution nanoflowers and their enhanced visible-light photocatalytic hydrogen-production performance.

Sustainable photocatalytic hydrogen evolution (PHE) of water splitting has been utilized to solve the serious environmental pollution and energy shortage problems over the last decade. Inorganic-organic hybrid materials could combine the organic molecules and functional inorganic blocks into unique materials through complicated physical and chemical interactions. In this paper, diethylenetriamine (DETA) was used as an organic molecule template for the synthesis of inorganic-organic Zn1-xCdxS-DETA solid solution nanoflowers (NFs) at very low temperature. The obtained Zn0.2Cd0.8S-DETA NFs exhibited the highest H2 production rate (12 718 µmol g-1 h-1), which is 1.75 times as high as that of CdS-DETA. The suitable conduction band potential and excellent visible-light absorption of Zn0.2Cd0.8S-DETA solid solution NFs are closely related to the excellent PHE activity. Furthermore, the calculation on the electronic structure provides a new understanding of the band-gap shifts of the Zn1-xCdxS-DETA solid solution hybrids and the design of novel structural photocatalysts.