Surface Coordination Environment Engineering on PtxCu1-x Alloy Catalysts for the Efficient Photocatalytic Reduction of CO2 to CH4.

Alloy catalysts have been reported to be robust in catalyzing various heterogeneous reactions due to the synergistic effect between different metal atoms. In this work, aimed at understanding the effect of the coordination environment of surface atoms on the catalytic performance of alloy catalysts, a series of PtxCu1-x alloy model catalysts supported on anatase-phase TiO2 (PtxCu1-x/Ti, x = 0.4, 0.5, 0.6, 0.8) were developed and applied in the classic photocatalytic CO2 reduction reaction. According to the results of catalytic performance evaluation, it was found that the photocatalytic CO2 reduction activity on PtxCu1-x/Ti showed a volcanic change as a function of the Pt/Cu ratio, the highest CO2 conversion was achieved on Pt0.5Cu0.5/Ti, with CH4 as the main product. Further systematic characterizations and theoretical calculations revealed that the equimolar amounts of Pt and Cu in Pt0.5Cu0.5/Ti facilitated the generation of more Cu-Pt-paired sites (i.e., the higher coordination number of Pt-Cu), which would favor a bridge adsorption configuration of CO2 and facilitate the electron transfer, thus resulting in the highest photocatalytic CO2 reduction efficiency on Pt0.5Cu0.5/Ti. This work provided new insights into the design of excellent CO2 reduction photocatalysts with high CH4 selectivity from the perspective of surface coordination environment engineering on alloy catalysts.

High photocatalytic performance over ultrathin 2D TiO2 for CO2 reduction to alcohols.

We report a noble-metal-free photocatalyst, ultrathin TiO2 with atomic layer thickness, which is a potential catalyst for CO2 photoreduction. An excellent liquid-product yield of 463.9 µmol gcat-1 in 8 h with 98% selectivity to alcohols was achieved, owing to sufficient surface defects favoring CO2 adsorption/activation.

Engineering Z-Scheme FeOOH/PCN with Fast Photoelectron Transfer and Surface Redox Kinetics for Efficient Solar-Driven CO2 Reduction.

Solar-driven conversion of carbon dioxide (CO2) without sacrificial agents offers an attractive alternative in sustainable energy research; nevertheless, it is often retarded by the sluggish water oxidation kinetics and severe charge recombination. To this end, a Z-scheme iron oxyhydroxide/polymeric carbon nitride (FeOOH/PCN) heterojunction, as identified by quasi in situ X-ray photoelectron spectroscopy, is constructed. In this heterostructure, the two-dimensional FeOOH nanorod provides rich coordinatively unsaturated sites and highly oxidative photoinduced holes to boost the sluggish water decomposition kinetics. Meanwhile, PCN acts as a robust agent for CO2 reduction. Consequently, FeOOH/PCN achieves efficient CO2 photoreduction with a superior selectivity of CH4 (>85%), together with an apparent quantum efficiency of 2.4% at 420 nm that outperforms most two-step photosystems to date. This work offers an innovative strategy for the construction of photocatalytic systems toward solar fuel production.

Engineering interfacial band bending over bismuth vanadate/carbon nitride by work function regulation for efficient solar-driven water splitting.

Nature-inspired artificial Z-scheme photocatalyst offers great promise in solar overall water splitting, but its rational design, construction and interfacial charge transfer mechanism remain ambiguous. Here, we design an approach of engineering interfacial band bending via work function regulation, which realizes directional charge transfer at interface and affords direct Z-scheme pathway. Taking BiVO4 as prototype, its oxygen vacancy concentration is reduced by slowing down the crystallization rate, thereby changing the work function from smaller to larger than that of polymeric carbon nitride (PCN). Consequently, the photoinduced charge transfer pathway of BiVO4/PCN is switched from type-II to Z-scheme as evidenced by synchronous illuminated X-ray photoelectron spectroscopy (XPS) and femtosecond transient absorption spectroscopy. Specifically, the direct Z-scheme BiVO4/PCN shows superior photocatalytic performance in water splitting. This work provides deep insights and guidelines to constructing heterojunction photocatalysts for solar utilization.

Low-Spin-State Hematite with Superior Adsorption of Anionic Contaminations for Water Purification.

Hematite attracts intensive interest as an adsorbent for water purification, but the oversized dimension and inherent high-spin Fe(III) restrict its adsorption capability and kinetics. Herein a spatial-confinement strategy is reported that synthesizes ultrafine α-Fe2 O3 benefiting from nanogrids constructed by predeposition of TiO2 nanodots in the MCM-41 channel, and that tunes the spin-state of Fe(III) from high-spin to low-spin induced by the strong guest-host interaction between the ultrafine Fe2 O3 with SiO2 (MCM-41). The low-spin Fe(III) endorses strong bonding with anionic adsorbates, and significantly facilitates the electrons transfer from Fe2 O3 to SiO2 to form a highly positive charged surface, and thereby shows superior electrostatic multilayer adsorption performance to different kinds of anionic contaminations. Specifically, the maximum uptake, adsorption rate, and distribution coefficient (Kd ) for Rose Bengal dye reach as high as 1810 mg g-1 , 1644 g (g min)-1 , and 2.2 × 106 L kg-1 , which are more than 8, 230, and 3700 times higher than those of commercial activated carbon, respectively. It also shows outstanding purification performance for real field water. It is demonstrated that a strong guest-host interaction can alter the spin-state of transition metal oxides, which may pave a new way to improve their performance in adsorption and other applications like catalysis.