Dual Lewis Acid-Base Sites Regulate Silver-Copper Bimetallic Oxide Nanowires for Highly Selective Photoreduction of Carbon Dioxide to Methane.

Highly selective photoreduction of CO2 to valuable hydrocarbons is of great importance to achieving a carbon-neutral society. Precisely manipulating the formation of the Metal1 ⋅⋅⋅C=O⋅⋅⋅Metal2 (M1 ⋅⋅⋅C=O⋅⋅⋅M2 ) intermediate on the photocatalyst interface is the most critical step for regulating selectivity, while still a significant challenge. Herein, inspired by the polar electronic structure feature of CO2 molecule, we propose a strategy whereby the Lewis acid-base dual sites confined in a bimetallic catalyst surface are conducive to forming a M1 ⋅⋅⋅C=O⋅⋅⋅M2 intermediate precisely, which can promote selectivity to hydrocarbon formation. Employing the Ag2 Cu2 O3 nanowires with abundant Cu⋅⋅⋅Ag Lewis acid-base dual sites on the preferred exposed {110} surface as a model catalyst, 100 % selectivity toward photoreduction of CO2 into CH4 has been achieved. Subsequent surface-quenching experiments and density functional theory (DFT) calculations verify that the Cu⋅⋅⋅Ag Lewis acid-base dual sites do play a vital role in regulating the M1 ⋅⋅⋅C=O⋅⋅⋅M2 intermediate formation that is considered to be prone to convert CO2 into hydrocarbons. This study reports a highly selective CO2 photocatalyst, which was designed on the basis of a newly proposed theory for precise regulation of reaction intermediates. Our findings will stimulate further research on dual-site catalyst design for CO2 reduction to hydrocarbons.

Interfacial Coordinational Bond Triggered Photoreduction Membrane for Continuous Light-Driven Precious Metals Recovery.

Chemical/electric energy-driven processes dominate the traditional precious metal (PM) recovery market. The renewable energy-driven selective PM recycling approach crucial for carbon neutrality is under exploration. Herein, via an interfacial structure engineering approach, coordinational-active pyridine groups are covalently integrated onto the photoactive semiconductor SnS2 surface to construct Py-SnS2. Triggered by the preferred coordinational binding force between PMs and pyridine groups, together with the photoreduction capability of SnS2, Py-SnS2 shows significantly enhanced selective PM-capturing performance toward Au3+, Pd4+, and Pt4+ with recycling capacity up to 1769.84, 1103.72, and 617.61 mg/g for Au3+, Pd4+, and Pt4+, respectively. Further integrating the Py-SnS2 membrane into a homemade light-driven flow cell, 96.3% recovery efficiency was achieved for continuous Au recycling from a computer processing unit (CPU) leachate. This study reported a novel strategy to fabricate coordinational bonds triggered photoreductive membranes for continuous PM recovery, which could be expanded to other photocatalysts for broad environmental applications.

Interfacial Coordination Bonding-Assisted Redox Mechanism-Driven Highly Selective Precious Metal Recovery on Covalent-Functionalized Ultrathin 1T-MoS2.

Rational design of functional material interfaces with well-defined physico-chemical-driven forces is crucial for achieving highly efficient interfacial chemical reaction dynamics for resource recovery. Herein, via an interfacial structure engineering strategy, precious metal (PM) coordination-active pyridine groups have been successfully covalently integrated into ultrathin 1T-MoS2 (Py-MoS2). The constructed Py-MoS2 shows highly selective interfacial coordination bonding-assisted redox (ICBAR) functionality toward PM recycling. Py-MoS2 shows state-of-the-art high recovery selectivity toward Au3+ and Pd4+ within 13 metal cation mixture solutions. The related recycling capacity reaches up to 3343.00 and 2330.74 mg/g for Au3+ and Pd4+, respectively. More importantly, above 90% recovery efficiencies have been achieved in representative PMs containing electronic solid waste leachate, such as computer processing units (CPU) and spent catalysts. The ICBAR mechanism developed here paves the way for interface engineering of the well-documented functional materials toward highly efficient PM recovery.

Photo-assisted reductive cleavage and catalytic hydrolysis-mediated persulfate activation by mixed redox-couple-involved CuFeS2 for efficient trichloroethylene oxidation in groundwater.

Persulfate (PS, S2O82-) activation through transition metal sulfides (TMS) has gained increasing attention since it can decompose a wide variety of refractory halogenated organic compounds in groundwater and wastewater. However, the processes of PS activation by TMS and particularly the formation of •OH radical under anoxic and acidic conditions (pH ∼2.8) remain elusive. Herein, by employing mixed redox-couple-involved chalcopyrite (CuFeS2) (150 mg/L) nanoparticles for PS (3.0 mM) activation, 96% of trichloroethylene was degraded within 120 min at pH 6.8 under visible light irradiation. The combination of experimental studies and theoretical calculations suggested that the Cu(I)/Fe(III) mixed redox-couple in CuFeS2 plays a crucial role to activate PS. Cu(I) acted as an electron donor to transfer electron to Fe(III), then Fe(III) served as an electron transfer bridge as well as a catalytic center to further donate this received electron to the O-O bond of PS, thus yielding SO4•- for trichloroethylene oxidation. Moreover, for the first time, •OH radicals were found to form from the catalytic hydrolysis of PS onto CuFeS2 surface, where S2O82- anion was hydrolyzed to yield H2O2 and these ensuing H2O2 were further transformed into •OH radicals via photoelectron-assisted O-O bond cleavage step. Our findings offer valuable insights for understanding the mechanisms of PS activation by redox-couple- involved TMS, which could promote the design of effective activators toward PS decomposition for environmental remediation.

Molecular Dynamics Beyond the Monolayer Adsorption as Derived from Langmuir Curve Fitting.

Langmuir adsorption model is a classic physical-chemical adsorption model and is widely used to describe the monolayer adsorption behavior at the material interface in environmental chemistry. Traditional adsorption dynamic modeling solely considered the surface physiochemical interaction between the adsorbent and adsorbate. The surface reaction dynamics resulting from the heterogeneous surface and intrinsic electronic structure of absorbents were rarely considered within the reported adsorption experiments. Herein, by employing the chlorine hybrid graphene oxide (GO-Cl) to adsorb Ag+ in an aqueous solution, complicated molecular dynamics significantly deviated from the monolayer adsorption mechanism, as suggested by Langmuir adsorption curve fitting, has been elucidated down to atomic scale. In the time-dependent Ag adsorption experiments, both Ag single atoms and Ag/AgCl nanoparticle heterostructures are observed to be formed sequentially on GO-Cl. These observations indicate that for the surface adsorption dynamics, not only the surface chemical adsorption process involved but also photoreduction and the C-Cl bond cleavage reaction has been heavily engaged within the GO-Cl interface, suggesting a much more complicated vision rather than the monolayered adsorption algorithm as derived from curve fitting. This study uses GO-Cl as a simple example to disclose the complicated adsorption dynamic process underneath Langmuir adsorption curve fitting. It advocates the necessity of imaging the interfacial atomic-scale dynamic structure with high-resolution microscopy techniques in modern adsorption studies, rather than simply explaining the adsorption dynamics relying on the curve fitting results due to the complicated physiochemical reactivity of the adsorbents.

Interfacial engineering of CuFeS2 quantum dots via platinum decoration with enhanced Cr(VI) reduction dynamics under UV-Vis-NIR radiation.

Configuring reactive and stable catalytic interfaces is crucial to design efficient photocatalysts for Cr(VI) reduction. Herein, via the platinum decoration approach based on interfacial engineering, we developed an effective catalytic interface within novel semiconducting chalcopyrite quantum dots (Pt/CuFeS2 QDs). Benefiting from the catalytic merits of the Pt modulated interfacial structure and electronic structure, Pt/CuFeS2 QDs show a broader light absorption capability extending to near-infrared radiation (NIR) range with superior carriers separation performance and faster charge transfer efficiency, which delivers a three-folder faster photocatalytic Cr(VI) reduction efficiency comparing to the original CuFeS2 QDs. Density functional theory (DFT) calculations unravel that Pt atoms prefer to be anchored with the surface S atoms to form a stable interfacial structure with faster electron transfer and Cr(VI) reduction dynamics. This work demonstrates that platinum decoration based on interfacial engineering is an effective strategy to simultaneously modulate the band structure and accelerate the interfacial reaction dynamics for semiconductor photocatalysts, which paves the way for designing highly efficient photocatalysts for light-driven environmental and energy engineering applications.

Protonation stabilized high As/F mobility red mud for Pb/As polluted soil remediation.

The hazardous red mud (RM) with high As/F mobility and heavy metal contaminated soil have constituted severe environmental threats. This work demonstrates a "waste to eco-material" strategy through a reliable and low-cost protonation approach to eliminate the As/F leaching risk of RM, and then recycle it as heavy metal passivators for Pb/As polluted soil remediation. The As/F anions have been immobilized by the protonated Fe/Al (hydr)oxides within RM via the formation of stable As/F compounds during the protonation process, which satisfies the requirement by the World Health Organization (As leaching <0.01 mg/L; F leaching <0.8 mg/L). Moreover, in the oilseed rape pot experiments, by adding 30 g/kg stabilized RM into Pb/As polluted soils (100 ~ 300 ppm), benefited from its large adsorption capacity, approximately 40.9 ~ 49.7% Pb and 40.8 ~ 54.8% As concentrations in the plant are reduced without adverse effects. The whole process for RM treatment and soil remediation is cost-effective, straightforward and eco-friendly without secondary pollution or soil degradation. This research provides a green chemical strategy to address both RM recycling and heavy metal contaminated soil remediation problems, which shows high economic feasibility and ecological benefits.