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1.
Sci Adv ; 10(25): eado2442, 2024 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-38905333

RESUMO

Atomically dispersed Pt-group metals are promising as nanocatalysts because of their unique geometric structures and ultrahigh atomic utilization. However, loading isolated Pt-group metals in single-atom alloys (SAAs) with distinctive bimetallic sites is challenging. In this study, we present amorphous mesoporous Ni boride (Ni-B) as an ideal substrate to uniformly disperse Pt atoms with tunable loadings (1.7 to 12.2 wt %). The effect of the morphology, composition, and crystal phase of the Ni-B host on the growth and dispersion of Pt atoms is discussed. The resulting amorphous Pt-Ni-B mesoporous nanospheres exhibit superior electrocatalytic H2 evolution performance in acidic media. This strategy holds the potential to synthesize a diverse library of mesoporous amorphous Pt-group SAAs, by leveraging functional amorphous nanostructured 3d transition-metal borides as substrates, thereby proposing a comprehensive strategy to control atomically dispersed Pt-group metals.

2.
J Am Chem Soc ; 2024 Jun 09.
Artigo em Inglês | MEDLINE | ID: mdl-38853354

RESUMO

A piezoelectric polymer membrane based on single metal atoms was demonstrated to be effective by anchoring isolated calcium (Ca) atoms on a composite of nitrogen-doped carbon and polyvinylidene fluoride (PVDF). The addition of Ca-atom-anchored carbon nanoparticles not only promotes the formation of the ß phase (from 29.8 to 56.3%), the most piezoelectrically active phase, in PVDF, but also introduces much higher porosity and hydrophilicity. Under ultrasonic excitation, the fabricated catalyst membrane demonstrates a record-high and stable dye decomposing rate of 0.11 min-1 and antibacterial efficiencies of 99.8%. Density functional theory calculations reveal that the primary contribution to catalytic activity arises from single-atom Ca doping and that a possible synergistic effect between PVDF and Ca atoms can improve the catalytic performance. It is shown that O2 molecules can be easily hydrogenated to produce ·OH on Ca-PVDF, and the local electric field provided by the ß-phase-PVDF might enhance the production of ·O2-. The proposed polymer membrane is expected to inspire the rational design of piezocatalysts and pave the way for the application of piezocatalysis technology for practical environmental remediation.

3.
Small ; : e2400611, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38488704

RESUMO

Although photocatalytic hydrogen production from water holds great potential as a renewable and sustainable energy alternative, the practical application of the technology demands cost-effective, simple photocatalytic systems with high efficiency in hydrogen evolution reaction (HER). Herein, the synthesis and characterization of Cu31 S16 /Znx Cd1-x S heterostructured nanoplates (Cu31 S16 /ZnCdS HNPs) as a high photocatalytic system are reported. The cost-effective, hierarchical structures are easily prepared using the Cu31 S16 NPs as the seed by the epitaxial growth of the ZnCdS nanocrystals (NCs). The Cu31 S16 /ZnCdS without the noble metal cocatalyst exhibits a high HER rate of 61.7 mmol g-1  h-1 , which is 8,014 and 17 times higher than that of Cu31 S16 and ZnCdS, respectively, under visible light irradiation. The apparent quantum yield (AQY) of Cu31 S16 /ZnCdS reaches 67.9% at 400 nm with the highest value so far in the reported ZnCdS-based photocatalysts. The excellent activity and stability of the Cu31 S16 /ZnCdS are attributed to the formation of a strong internal electric field (IEF) and the Z-scheme pathway. The comprehensive experiments and theoretical calculations provide the direct evidences of the Z-scheme route. This work may offer a way for the design and development of efficient photocatalysts to achieve solar-to-chemical energy conversion at a practically useful level.

4.
Angew Chem Int Ed Engl ; 63(18): e202401884, 2024 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-38376362

RESUMO

The exfoliation of bulk C3N4 (BCN) into ultrathin layered structure is an effective strategy to boost photocatalytic efficiency by exposing interior active sites and accelerating charge separation and transportation. Herein, we report a novel nitrate anion intercalation-decomposition (NID) strategy that is effective in peeling off BCN into few-layer C3N4 (fl-CN) with tailored thickness down to bi-layer. This strategy only involves hydrothermal treatment of BCN in diluted HNO3 aqueous solution, followed by pyrolysis at various temperatures. The decomposition of the nitrate anions not only exfoliates BCN and changes the band structure, but also incorporates oxygen species onto fl-CN, which is conducive to O2 adsorption and hence relevant chemical processes. In photocatalytic O2 reduction under visible light irradiation, the H2O2 production rate over the optimal fl-CN-530 catalyst is 952 µmol g-1 h-1, which is 8.8 times that over BCN. More importantly, under full arc irradiation and in the absence of hole scavenger, CH4 can be photocatalytically oxidized by on-site formed H2O2 and active oxygen species to generate value-added C1 oxygenates with high selectivity of 99.2 % and record-high production rate of 1893 µmol g-1 h-1 among the metal-free C3N4-based photocatalysts.

5.
RSC Adv ; 14(10): 6502-6507, 2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38390506

RESUMO

Direct CO2 hydrogenation to value-added chemicals is a promising path toward realizing the "carbon-neutral" goal. However, controlling the selectivity of CO2 hydrogenation toward desired products (e.g., CO and CH4) using non-precious metal-based catalysts is important but challenging. It is imperative to explore catalysts with high activity and stability. Herein, boron-doped cobalt nanoparticles supported on H-ZSM-5 were devised for CO2 hydrogenation to produce CO in a gas-solid flow system. Our results demonstrate that boron doping not only increases the CO2 adsorption capability of the catalyst but also optimizes the electronic state of Co for CO desorption during hydrogenation process. As a result, the boron-doped cobalt catalysts displayed an enhanced CO selectivity of 94.5% and a CO2 conversion rate of 45.6%, which is much higher than that of Co-ZSM-5 without boron doping. This study shows that the strategic design of metal borides is important for controlling the selectivity of desired products in the CO2 hydrogenation reaction.

6.
Angew Chem Int Ed Engl ; 63(8): e202318927, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38189599

RESUMO

Achieving the complete mineralization of persistent pollutants in wastewater is still a big challenge. Here, we propose an efficient photo-self-Fenton reaction for the degradation of different pollutants using the high-density (Ag: 22 wt %) of atomically dispersed AgCo dual sites embedded in graphic carbon nitride (AgCo-CN). Comprehensive experimental measurements and density functional theory (DFT) calculations demonstrate that the Ag and Co dual sites in AgCo-CN play a critical role in accelerating the photoinduced charge separation and forming the self-Fenton redox centers, respectively. The bimetallic AgCo-CN exhibited excellent photocatalytic performance toward the phenol even under extreme conditions due to an efficient degradation pathway and in situ generation of the hydrogen peroxide producing the main active oxygen species (⋅OH and 1 O2 ) and showed long-term activity in a self-design photo-Filter reactor for the purification of the phenol. Our discoveries pave the way for the design of efficient single-atoms photocatalysts-based photo-self-Fenton reaction for recalcitrant pollutant treatment.

7.
J Environ Sci (China) ; 134: 11-20, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37673526

RESUMO

Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported a novel Fe2O3/TiO2/reduced graphene oxide (FTG) nanocomposite synthesized by a facile solvothermal method. The TiO2 in FTG degraded organic pollutants and mineralized intermediates via photocatalysis under visible light irradiation, which could also promote Fenton reaction by accelerating Fe3+-Fe2+ recycle. Meanwhile, the Fe2O3 rapidly degraded organic pollutants via Fenton reactions, which also promoted photocatalysis by enhancing visible light absorbance and diminishing photoelectron-hole recombination. The high distribution of TiO2 and Fe2O3 on rGO, together with their strong interaction resulted in enhanced synergetic cooperation between photocatalysis and Fenton reactions, leading to the high mineralization efficiency of organic pollutants. More importantly, it could also inhibit the leaching of Fe species, leading to the long lifetime of FTG during photocatalytic Fenton reactions in a wide pH range from 3.4 to 9.2.


Assuntos
Poluentes Ambientais , Grafite , Concentração de Íons de Hidrogênio
8.
Angew Chem Int Ed Engl ; 62(45): e202312734, 2023 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-37735738

RESUMO

Single-atom catalysts (SACs) have emerged as crucial players in catalysis research, prompting extensive investigation and application. The precise control of metal atom nucleation and growth has garnered significant attention. In this study, we present a straightforward approach for preparing SACs utilizing a photocatalytic radical control strategy. Notably, we demonstrate for the first time that radicals generated during the photochemical process effectively hinder the aggregation of individual atoms. By leveraging the cooperative anchoring of nitrogen atoms and crystal lattice oxygen on the support, we successfully stabilize the single atom. Our Pd1 /TiO2 catalysts exhibit remarkable catalytic activity and stability in the Suzuki-Miyaura cross-coupling reaction, which was 43 times higher than Pd/C. Furthermore, we successfully depose Pd atoms onto various substrates, including TiO2 , CeO2 , and WO3 . The photocatalytic radical control strategy can be extended to other single-atom catalysts, such as Ir, Pt, Rh, and Ru, underscoring its broad applicability.

9.
J Am Chem Soc ; 145(28): 15482-15487, 2023 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-37418381

RESUMO

Efficient utilization of infrared (IR) light, which occupies almost half of the solar energy, is an important but challenging task in solar-to-fuel transformation. Herein, we report the discovery of CuS@ZnS core@shell nanocrystals (CSNCs) with strong localized surface plasmon resonance (LSPR) characteristics in the IR light region showing enhanced photocatalytic activity in hydrogen evolution reaction (HER). A unique "plasmon-induced defect-mediated carrier transfer" (PIDCT) at the heterointerfaces of the CSNCs divulged by time-resolved transient spectroscopy enables producing a high quantum yield of 29.2%. The CuS@ZnS CSNCs exhibit high activity and stability in H2 evolution under near-IR light irradiation. The HER rate of CuS@ZnS CSNCs at 26.9 µmol h-1 g-1 is significantly higher than those of CuS NCs (0.4 µmol h-1 g-1) and CuS/ZnS core/satellite heterostructured NCs (15.6 µmol h-1 g-1). The PIDCT may provide a viable strategy for the tuning of LSPR-generated carrier kinetics through controlling the defect engineering to improve photocatalytic performance.

10.
ACS Nano ; 17(14): 13017-13043, 2023 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-37367960

RESUMO

Controlling the synthesis of metal nanostructures is one approach for catalyst engineering and performance optimization in electrocatalysis. As an emerging class of unconventional electrocatalysts, two-dimensional (2D) metallene electrocatalysts with ultrathin sheet-like morphology have gained ever-growing attention and exhibited superior performance in electrocatalysis owing to their distinctive properties originating from structural anisotropy, rich surface chemistry, and efficient mass diffusion capability. Many significant advances in synthetic methods and electrocatalytic applications for 2D metallenes have been obtained in recent years. Therefore, an in-depth review summarizing the progress in developing 2D metallenes for electrochemical applications is highly needed. Unlike most reported reviews on the 2D metallenes, this review starts by introducing the preparation of 2D metallenes based on the classification of the metals (e.g., noble metals, and non-noble metals) instead of synthetic methods. Some typical strategies for preparing each kind of metal are enumerated in detail. Then, the utilization of 2D metallenes in electrocatalytic applications, especially in the electrocatalytic conversion reactions, including the hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, fuel oxidation reaction, CO2 reduction reaction, and N2 reduction reaction, are comprehensively discussed. Finally, current challenges and opportunities for future research on metallenes in electrochemical energy conversion are proposed.

11.
RSC Adv ; 13(23): 15998, 2023 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-37250224

RESUMO

[This corrects the article DOI: 10.1039/D0RA03959D.].

12.
Angew Chem Int Ed Engl ; 62(28): e202305538, 2023 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-37191471

RESUMO

The selective conversion of dilute NO pollutant into low-toxic product and simultaneous storage of metabolic nitrogen for crop plants remains a great challenge from the perspective of waste management and sustainable chemistry. This study demonstrates that this bottleneck can be well tackled by refining the reactive oxygen species (ROS) on Ni-modified NH2 -UiO-66(Zr) (Ni@NU) using nickel foam (NF) as a three-dimensional (3D) substrate through a flow photoanode reactor via the gas-phase photoelectrocatalysis. By rationally refining the ROS to ⋅OH, Ni@NU/NF can rapidly eliminate 82 % of NO without releasing remarkable NO2 under a low bias voltage (0.3 V) and visible light irradiation. The abundant mesoporous pores on Ni@NU/NF are conducive to the diffusion and storage of the formed nitrate, which enables the progressive conversion NO into nitrate with selectivity over 99 % for long-term use. Through calculation, 90 % of NO could be recovered as the nitrate species, indicating that this state-of-the-art strategy can capture, enrich and recycle the pollutant N source from the atmosphere. This study offers a new perspective of NO pollutant treatment and sustainable nitrogen exploitation, which may possess great potential to the development of highly efficient air purification systems for industrial and indoor NOx control.

13.
Nat Commun ; 14(1): 2534, 2023 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-37137896

RESUMO

The photoreduction of carbon dioxide (CO2) into renewable synthetic fuels is an attractive approach for generating alternative energy feedstocks that may compete with and eventually displace fossil fuels. However, it is challenging to accurately trace the products of CO2 photoreduction on account of the poor conversion efficiency of these reactions and the imperceptible introduced carbon contamination. Isotope-tracing experiments have been used to solve this problem, but they frequently yield false-positive results because of improper experimental execution and, in some cases, insufficient rigor. Thus, it is imperative that accurate and effective strategies for evaluating various potential products of CO2 photoreduction are developed for the field. Herein, we experimentally demonstrate that the contemporary approach toward isotope-tracing experiments in CO2 photoreduction is not necessarily rigorous. Several examples of where pitfalls and misunderstandings arise, consequently making isotope product traceability difficult, are demonstrated. Further, we develop and describe standard guidelines for isotope-tracing experiments in CO2 photoreduction reactions and then verify the procedure using some reported photoreduction systems.

14.
J Am Chem Soc ; 145(11): 6079-6086, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36855832

RESUMO

Amorphous noble metals with high surface areas have attracted significant interest as heterogeneous catalysts due to the numerous dangling bonds and abundant unsaturated surface atoms created by the amorphous phase. However, synthesizing amorphous noble metals with high surface areas remains a significant challenge due to strong isotropic metallic bonds. This paper describes the first example of a mesoporous amorphous noble metal alloy [iridium-tellurium (IrTe)] obtained using a micelle-directed synthesis method. The resulting mesoporous amorphous IrTe electrocatalyst exhibits excellent performance in the electrochemical N2 reduction reaction. The ammonia yield rate is 34.6 µg mg-1 h-1 with a Faradaic efficiency of 11.2% at -0.15 V versus reversible hydrogen electrode in 0.1 M HCl solution, outperforming comparable crystalline and Ir metal counterparts. The interconnected porous scaffold and amorphous nature of the alloy create a complementary effect that simultaneously enhances N2 absorption and suppresses the hydrogen evolution reaction. According to theoretical simulations, incorporating Te in the IrTe alloy effectively strengthens the adsorption of N2 and lowers the Gibbs free energy for the rate-limiting step of the electrocatalytic N2 reduction reaction. Mesoporous chemistry enables a new route to achieve high-performance amorphous metalloid alloys with properties that facilitate the selective electrocatalytic reduction of N2.

15.
Front Chem ; 11: 1124303, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36874073

RESUMO

The influence of metal ions, the state of metal salt, and ligands on the sterilization ability of (Metalorganic frameworks) MOFs to effectively achieve sterilization has been investigated in this study. Initially, the MOFs were synthesized by elements of Zn, Ag, and Cd for the same periodic and main group of Cu. This illustrated that the atomic structure of Cu was more beneficial for coordinating with ligands. To further induce the maximum amount of Cu2+ ions in the Cu-MOFs to achieve the highest sterilization, various Cu-MOFs synthesized by the different valences of Cu, various states of copper salts, and organic ligands were performed, respectively. The results demonstrated that Cu-MOFs synthesized by 3, 5-dimethyl-1, 2, 4-triazole and tetrakis (acetonitrile) copper(I) tetrafluoroborate presented the largest inhibition-zone diameter of 40.17 mm towards Staphylococcus Aureus (S. aureus) under dark conditions. The proposed mechanism of Cu (Ⅱ) in MOFs could significantly cause multiple toxic effects, such as the generation of reactive oxygen species, and lipid peroxidation in S. aureus cells, when the bacteria was anchored by the Cu-MOFs via electrostatic interaction. Finally, the broad antimicrobial properties of Cu-MOFs against Escherichia coli (E. coli), Acinetobacter baumannii (A. baumannii), and S. aureus were demonstrated. In conclusion, the Cu-3, 5-dimethyl-1, 2, 4-triazole MOFs appeared to be potential antibacterial catalysts in the antimicrobial field.

16.
Nanoscale ; 15(14): 6709-6721, 2023 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-36938843

RESUMO

Efficient removal of air pollution caused by volatile organic compounds (VOCs) and particulate matter (PM) through distributed energy collected from the environment is an effective strategy to achieve both energy conservation and better air quality. Herein, a curtain purification system based on a rabbit fur-based rotary triboelectric nanogenerator (RR-TENG) and a collaborative photocatalysis technology was designed for indoor air purification. The high electrostatic field from RR-TENG enhances formaldehyde adsorption, while it can also efficiently adsorb PM2.5 simultaneously. More interestingly, the ultrahigh electric field provided by RR-TENG promotes the separation of photogenerated electron-hole pairs of the g-C3N4/TiO2 composite photocatalyst, generating more superoxide radicals (⋅O2-), hydroxyl radicals (⋅OH), and holes (h+) and thereby improving the photocatalytic efficiency. In a simulated reaction chamber of 9 L, the formaldehyde removal rate of the system can reach 79.2% within 90 min and RR-TENG rapidly reduces PM2.5 from 999 µg m-3 to 50 µg m-3 within 60 s. This study proposes a curtain purification system integrating the function of energy collection and photocatalytic purification, which can be applied for improving air quality and human health.

17.
Angew Chem Int Ed Engl ; 62(18): e202302202, 2023 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-36866944

RESUMO

Designing adsorption materials with high adsorption capacities and selectivities is highly desirable for precious metal recovery. Desorption performance is also particularly crucial for subsequent precious metal recovery and adsorbent regeneration. Herein, a metal-organic framework (MOF) material (NH2 -UiO-66) with an asymmetric electronic structure of the central zirconium oxygen cluster has an exceptional gold extraction capacity of 2.04 g g-1 under light irradiation. The selectivity of NH2 -UiO-66 for gold ions is up to 98.8 % in the presence of interfering ions. Interestingly, the gold ions adsorbed on the surface of NH2 -UiO-66 spontaneously reduce in situ, undergo nucleation and growth and finally achieve the phase separation of high-purity gold particles from NH2 -UiO-66. The desorption and separation efficiency of gold particles from the adsorbent surface reaches 89 %. Theoretical calculations indicate that -NH2 functions as a dual donor of electrons and protons, and the asymmetric structure of NH2 -UiO-66 leads to energetically advantageous multinuclear gold capture and desorption. This adsorption material can greatly facilitate the recovery of gold from wastewater and can easily realize the recycling of the adsorbent.

18.
ACS Nano ; 17(4): 3346-3357, 2023 02 28.
Artigo em Inglês | MEDLINE | ID: mdl-36744876

RESUMO

Construction of a well-defined mesoporous nanostructure is crucial for applying nonnoble metals in catalysis and biomedicine owing to their highly exposed active sites and accessible surfaces. However, it remains a great challenge to controllably synthesize superparamagnetic CoFe-based mesoporous nanospheres with tunable compositions and exposed large pores, which are sought for immobilization or adsorption of guest molecules for magnetic capture, isolation, preconcentration, and purification. Herein, a facile assembly strategy of a block copolymer was developed to fabricate a mesoporous CoFeB amorphous alloy with abundant metallic Co/Fe atoms, which served as an ideal scaffold for well-dispersed loading of Au nanoparticles (∼3.1 nm) via the galvanic replacement reaction. The prepared Au-CoFeB possessed high saturation magnetization as well as uniform and large open mesopores (∼12.5 nm), which provided ample accessibility to biomolecules, such as nucleic acids, enzymes, proteins, and antibodies. Through this distinctive combination of superparamagnetism (CoFeB) and biofavorability (Au), the resulting Au-CoFeB was employed as a dispersible nanovehicle for the direct capture and isolation of p53 autoantibody from serum samples. Highly sensitive detection of the autoantibody was achieved with a limit of detection of 0.006 U/mL, which was 50 times lower than that of the conventional p53-ELISA kit-based detection system. Our assay is capable of quantifying differential expression patterns for detecting p53 autoantibodies in ovarian cancer patients. This assay provides a rapid, inexpensive, and portable platform with the potential to detect a wide range of clinically relevant protein biomarkers.


Assuntos
Nanopartículas Metálicas , Feminino , Humanos , Nanopartículas Metálicas/química , Autoanticorpos , Ouro/química , Proteína Supressora de Tumor p53 , Nanopartículas Magnéticas de Óxido de Ferro
19.
Artigo em Inglês | MEDLINE | ID: mdl-36749108

RESUMO

Oxygen reduction and evolution reactions (ORR and OER, respectively) are vital steps for metal-air batteries, which are plagued by their sluggish kinetics. It is still a challenge to develop highly effective and low-cost non-noble-metal-based electrocatalysts. Herein, a simple and reliable method was reported to synthesize a Co2P-assisted Co single-atom (Co-N4 centers) electrocatalyst (Co2P/Co-NC) via evaporative drying and pyrolysis processes. The Co2P nanoparticles and Co-N4 centers are uniformly distributed on the nitrogen-doped carbon matrix. Notably, Co2P/Co-NC showed excellent activities in both ORR (initial potential, 1.01 V; half-wave potential, 0.88 V) and OER (overpotential, 369 mV at 10 mA cm-2). The above results were comparable to those of commercial catalysts (such as Pt/C and RuO2). Based on the experimental and theoretical analyses, the impressive activity can be ascribed to the tailored electronic structure of Co-N4 centers by the adjacent Co2P, enabling the electron transfer from the Co atom to the neighboring C atoms, leading to a downshift of the d-band center, and improved reaction kinetics were achieved. The assembled Zn-air batteries using Co2P/Co-NC as the air cathode showed a peak power density of 187 mW cm-2 and long-life cycling stability for 140 h at 5 mA cm-2. This work may pave a promising avenue to design hybrid bifunctional electrocatalysts for highly efficient ORR/OER.

20.
Angew Chem Int Ed Engl ; 62(6): e202215574, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36479970

RESUMO

The design for non-Cu-based catalysts with the function of producing C2+ products requires systematic knowledge of the intrinsic connection between the surface state as well as the catalytic activity and selectivity. In this work, photochemical in situ spectral surface characterization techniques combined with the first principle calculations (DFT) were applied to investigate the relationships between the composition of surface states, coordinated motifs, and catalytic selectivity of a titanium oxynitride catalyst. When the catalyst mediates CO2 photoreduction, C2 product selectivity is positively correlated with the surface Ti2+ /Ti3+ ratio and the surface oxidation state is regulated and controlled by coordinated motifs of N-Ti-O/V[O], which can reduce the potential dimerization energy barriers of *CO-CO* and promote spontaneous formation of the subsequent *CO-CH2 * intermediate. This phenomenon provides a new perspective for the design of heterogeneous catalysts for photoreduction of CO2 into useful products.

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