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A coupling catalyst of highly dispersed N, P co-doped carbon frames (NPCFs) anchored with Fe single atoms (SAs) and Fe

Photocatalysis based on the use of semiconducting materials is an emerging alternative to conventional thermochemical catalysis, and it has the potential to promote chemical synthesis under greener and milder conditions. However, heterogeneous photocatalytic organic reactions are still in their infancy, limited by the low-efficiency carrier separation of the currently available photocatalytic materials. Here, we report photochromic Bi2WO6–x/amorphous BiOCl (p-BWO) nanosheets, which, distinct from pristine Bi2WO6, show blue colouration upon visible light irradiation and are bleached by atmospheric oxygen. Studies on the microscopic structure of the material reveal the existence of abundant W(vi)O6–x units, which serve as the sites for the fast and continuous consumption of photogenerated electrons, thereby effectively facilitating the separation of electron–hole pairs. The prepared composite features a remarkable enhancement in performance for the photocatalytic oxidation of toluene with a conversion rate 166-fold higher compared with that of pristine Bi2WO6. Despite its potential, the visible light-triggered photocatalytic oxidation of toluene remains difficult due to the lack of efficient and scalable catalytic strategies. Now, a photochromic Bi2WO6–x/amorphous BiOCl composite is reported with the ability to oxidize toluene into benzaldehyde and benzoic acid with outstanding rates and quantum efficiencies.

Developing an efficient single-atom material (SAM) synthesis and exploring the energy-related catalytic reaction are important but still challenging. A polymerization-pyrolysis-evaporation (PPE) strategy was developed to synthesize N-doped porous carbon (NPC) with anchored atomically dispersed Fe-N4 catalytic sites. This material was derived from predesigned bimetallic Zn/Fe polyphthalocyanine. Experiments and calculations demonstrate the formed Fe-N4 site exhibits superior trifunctional electrocatalytic performance for oxygen reduction, oxygen evolution, and hydrogen evolution reactions. In overall water splitting and rechargeable Zn-air battery devices containing the Fe-N4 SAs/NPC catalyst, it exhibits high efficiency and extraordinary stability. This current PPE method is a general strategy for preparing M SAs/NPC (M=Co, Ni, Mn), bringing new perspectives for designing various SAMs for catalytic application.

The promoting effect of sulfur sources is an intriguing but poorly understood phenomenon. Herein, we studied the treatment of PdCu bimetallic nanoparticles (NPs) with different amounts of sulfur powder. Low-level sulfidation led to the generation of a Pd30Cu10S9 NP catalyst consisting of surface enriched Pd NPs, electron deficient Pd and Cu, as well as zero valence sulfur. The Pd30Cu10S9 NP catalyst showed pronouncedly enhanced activity and selectivity in the semihydrogenation of alkynes. Our study revealed for the first time a possible cause for the promoting effect of sulfur at the atomic level, suggesting a new strategy in catalyst design.

RuCu nanocages and core–shell Cu@Ru nanocrystals with ultrathin Ru shells were first synthesized by a one-pot modified galvanic replacement reaction. The construction of bimetallic nanocrystals with fully exposed precious atoms and a high surface area effectively realizes the concept of high atom-efficiency. Compared with the monometallic Ru/C catalyst, both the RuCu nanocages and Cu@Ru core–shell catalysts supported on commercial carbon show superior catalytic performance for the regioselective hydrogenation of quinoline toward 1,2,3,4-tetrahydroquinoline. RuCu nanocages exhibit the highest activity, achieving up to 99.6% conversion of quinoline and 100% selectivity toward 1,2,3,4-tetrahydroquinoline.

Aqueous Ag:ZnCdS quantum dots (QDs) with pure, color-tunable fluorescence were prepared based on co-nucleation doping strategy by using a highly reactive S powder precursor, which was reduced by NaBH 4 at high temperature of 180 °C in a closed hydrothermal autoclave. For a meaningful comparison, thiourea as a relatively low reactive precursor was employed to test the advantages of this highly reactive S powder precursor in synthetic chemistry. The influences of various experimental variables, including the Zn/Cd ratio and Ag-doping concentration, on the optical properties of Ag:ZnCdS QDs were systematically investigated. The color-tunable quarternary Ag:ZnCdSeS QDs were also successfully prepared via the variation of Se/S precursor ratio based on the similar reactivity of the Se and S powder precursors. Further, the highly efficient Ag:ZnCdS/ZnS and Ag:ZnCdSeS/ZnS core/shell QDs were constructed by the deposition of the ZnS shell around the crude Ag:ZnCdS and Ag:ZnCdSeS core QDs. The results indicated that this facile synthetic route would provide a versatile approach for preparation of other aqueous multinary metal chalcogenide QDs.

High-quality, pure, and color-tunable Ag:ZnCdS quantum dots (d-dots) are prepared by optimization of the experimental conditions including Ag-doping concentration and Zn/Cd precursor ratio. Highly emissive Ag:ZnCdS/ZnS core/shell d-dots with photoluminescence quantum yield (PL QY) as high as 58% are constructed in situ by the growth of a ZnS shell around the crude Ag:ZnCdS solution, which is the highest PL QY reported to date for Ag-based semiconductor d-dots. The emission color of a Ag:ZnCdS d-dot can be tuned toward a larger red region by simple Se treatment at high temperature (220–260 °C). With Se treatment, Ag:ZnCdS alloyed d-dots are transformed into Ag:ZnCdSSe alloyed d-dots, and the corresponding optical changes of d-dots in this process are investigated systematically. This strategy provides a versatile approach for the preparation of other multinary semiconductor nanocrystals.

Based on a phosphine-free route and the nucleation-doping strategy, Mn-doped CdSe nanocrystals (d-dots) with zinc-blende structure were successfully synthesized by facilely controlling the reaction temperature. The evolution of the UV–vis and PL spectra exhibited the distinctly different results for the nanocrystals synthesized at 160,180 and 200 °C. The products were Mn:CdSe d-dots at 160 °C, but undoped CdSe nanocrystals at 200 °C. We proposed a possible mechanism that Mn ions were rapidly ejected from the host CdSe lattice if the doping temperature was too high. Combining with TEM and spectral results of the resulting nanocrystals, the mechanism was further confirmed powerfully by the annealing for the presynthesized and purified Mn:CdSe nanocrystals.

Water-soluble, highly emissive, color-tunable, and stable Cu:ZnSeS/ZnS core/shell doped nanocrystals (d-dots) with pure dopant emission have been synthesized through a simple aqueous synthetic route. The influence of various experimental variables, including introduction of chloride ions, amount of mercaptopropanoic acid (MPA), pH value and Cu-doping concentration, on the optical properties of Cu dopant emission have been systematically investigated. Through epitaxial growth of a ZnS shell on Cu:ZnSeS cores, the fabricated Cu:ZnSeS/ZnS d-dots exhibit a high PL QY of up to 40%, which is the highest ever reported for any type of water-soluble Cu-doped selenide-based II–VI semiconductor nanocrystals (NCs). Moreover, the serious photostability problem of Cu-based d-dots in the presence of air and light is solved and the quenching of the excitonic emission is suppressed as well. The stable testing of these highly luminescent d-dots shows that the Cu:ZnSeS/ZnS d-dots have better photostability and preserve more than ~90% of the initial intensity in the presence of air and light 30 days later. This new class of green emissive material shows their potential applications in biolabeling, bioimaging, and light emitting devices.