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Green plants convert sunlight into high-energy chemicals by coupling solar-driven water oxidation in the Z-scheme and CO2 fixation in the Calvin cycle. In this study, formate dehydrogenase from Clostridium ljungdahlii (ClFDH) is interfaced with a TiO2 -coated CuFeO2 and CuO mixed (ClFDH-TiO2 |CFO) electrode. In this biohybrid photocathode, the TiO2 layer enhances the photoelectrochemical (PEC) stability of the labile CFO photocathode and facilitates the transfer of photoexcited electrons from the CFO to ClFDH. Furthermore, inspired by the natural photosynthetic scheme, the photobiocathode is combined with a water-oxidizing, FeOOH-coated BiVO4 (FeOOH|BiVO4 ) photoanode to assemble a wireless Z-scheme biocatalytic PEC device as a semi-artificial leaf. The leaf-like structure effects a bias-free biocatalytic CO2 -to-formate conversion under visible light. Its rate of formate production is 2.45 times faster than that without ClFDH. This work is the first example of a wireless solar-driven semi-biological PEC system for CO2 reduction that uses water as an electron feedstock.

A robust photovoltaic (PV) is essential for long-term redox biotransformations in biocatalytic photoelectrochemical (PEC) platforms. Here, we report a single Cu(In,Ga)Se2 (CIGS) solar cell for unbiased photobiocatalytic reduction reactions. The photoanode/CIGS/cathode tandem assembly drives cofactor-dependent biocatalytic CO2 reduction under visible light. Our scalable PEC-PV tandem device achieves the longest reaction time of 72 h and the highest ever recorded turnover frequency and total turnover number of the cofactor of 0.236 h−1 and 11.2, respectively, for biocatalytic PEC production of formate through cofactor regeneration. This benchmark performance is attributed to the excellent PEC stability of the CIGS component; the substitution of CIGS with a perovskite solar cell (PSC) results in unstable generation of photocurrent and a lower concentration of formate under high-humidity environments because of the water-induced degradation of PSC. This work demonstrates the propriety of CIGS in robust PEC-PV tandems for artificial photosynthesis.

The electrocatalytic reduction of CO2 under low overpotential and mild conditions using redox enzyme is a propitious route for carbon capture and conversion. Here, we report bioelectrocatalytic CO2...

Significance The North China Plain experiences severe summer ozone pollution, but ozone during winter haze (particulate) pollution events has been very low. Here, we show that the abrupt decrease in nitrogen oxide (NOx) emissions following the COVID-19 lockdown in January 2020 drove fast ozone production during winter haze events to levels approaching the air quality standard. This fast ozone production was driven by formaldehyde originating from high emissions of volatile organic compounds (VOCs). The COVID-19 experience highlights a general 2013 to 2019 trend of rapidly increasing ozone pollution in winter–spring in China as NOx emissions have decreased. VOC emission controls would mitigate the spreading of ozone pollution into winter–spring with benefits for public health, crop production, and particulate pollution., Surface ozone is a severe air pollution problem in the North China Plain, which is home to 300 million people. Ozone concentrations are highest in summer, driven by fast photochemical production of hydrogen oxide radicals (HOx) that can overcome the radical titration caused by high emissions of nitrogen oxides (NOx) from fuel combustion. Ozone has been very low during winter haze (particulate) pollution episodes. However, the abrupt decrease of NOx emissions following the COVID-19 lockdown in January 2020 reveals a switch to fast ozone production during winter haze episodes with maximum daily 8-h average (MDA8) ozone concentrations of 60 to 70 parts per billion. We reproduce this switch with the GEOS-Chem model, where the fast production of ozone is driven by HOx radicals from photolysis of formaldehyde, overcoming radical titration from the decreased NOx emissions. Formaldehyde is produced by oxidation of reactive volatile organic compounds (VOCs), which have very high emissions in the North China Plain. This remarkable switch to an ozone-producing regime in January–February following the lockdown illustrates a more general tendency from 2013 to 2019 of increasing winter–spring ozone in the North China Plain and increasing association of high ozone with winter haze events, as pollution control efforts have targeted NOx emissions (30% decrease) while VOC emissions have remained constant. Decreasing VOC emissions would avoid further spreading of severe ozone pollution events into the winter–spring season.

Redox enzymes catalyze fascinating chemical reactions with excellent regio- and stereo-specificity. Nicotinamide adenine dinucleotide cofactor is essential in numerous redox biocatalytic reactions and needs to be regenerated because it is consumed as an equivalent during the enzymatic turnover. Here we report on unbiased photoelectrochemical tandem assembly of a photoanode (FeOOH/BiVO4) and a perovskite photovoltaic to provide sufficient potential for cofactor-dependent biocatalytic reactions. We obtain a high faradaic efficiency of 96.2% and an initial conversion rate of 2.4 mM h−1 without an external applied bias for the photoelectrochemical enzymatic conversion of α-ketoglutarate to l-glutamate via l-glutamate dehydrogenase. In addition, we achieve a total turnover number and a turnover frequency of the enzyme of 108,800 and 6200 h−1, respectively, demonstrating that the tandem configuration facilitates redox biocatalysis using light as the only energy source. Photoelectrochemical (PEC) cell platforms typically need an electrical bias that drives the electron transfer from the photoanode to the photocathode. Here, the authors report a bias-free PEC tandem device for solar-driven redox biocatalysis.

Biocatalytic transformation has received increasing attention in the green synthesis of chemicals because of the diversity of enzymes, their high catalytic activities and specificities, and mild reaction conditions. The idea of solar energy utilization in chemical synthesis through the combination of photocatalysis and biocatalysis provides an opportunity to make the "green" process greener. Oxidoreductases catalyze redox transformation of substrates by exchanging electrons at the enzyme's active site, often with the aid of electron mediator(s) as a counterpart. Recent progress indicates that photoinduced electron transfer using organic (or inorganic) photosensitizers can activate a wide spectrum of redox enzymes to catalyze fuel-forming reactions (e.g., H2 evolution, CO2 reduction) and synthetically useful reductions (e.g., asymmetric reduction, oxygenation, hydroxylation, epoxidation, Baeyer-Villiger oxidation). This Review provides an overview of recent advances in light-driven activation of redox enzymes through direct or indirect transfer of photoinduced electrons.

Natural photosynthesis is an effective route for the clean and sustainable conversion of CO2 into high-energy chemicals. Inspired by the natural process, a tandem photoelectrochemical (PEC) cell with an integrated enzyme-cascade (TPIEC) system was designed, which transfers photogenerated electrons to a multienzyme cascade for the biocatalyzed reduction of CO2 to methanol. A hematite photoanode and a bismuth ferrite photocathode were applied to fabricate the iron oxide based tandem PEC cell for visible-light-assisted regeneration of the nicotinamide cofactor (NADH). The cell utilized water as an electron donor and spontaneously regenerated NADH. To complete the TPIEC system, a superior three-dehydrogenase cascade system was employed in the cathodic part of the PEC cell. Under applied bias, the TPIEC system achieved a high methanol conversion output of 220 μm h−1, 1280 μmol g−1 h−1 using readily available solar energy and water.

Herein, we report a siloxane-encapsulated upconversion nanoparticle hybrid composite (SE-UCNP), which exhibits excellent photoluminescence (PL) stability for over 40 days even at an elevated temperature, in high humidity, and in harsh chemicals. The SE-UCNP is synthesized through UV-induced free-radical polymerization of a sol-gel-derived UCNP-containing oligosiloxane resin (UCNP-oligosiloxane). The siloxane matrix with a random network structure by Si-O-Si bonds successfully encapsulates the UCNPs with chemical linkages between the siloxane matrix and organic ligands on UCNPs. This encapsulation results in surface passivation retaining the intrinsic fluorescent properties of UCNPs under severe conditions (e.g., 85 °C/85% relative humidity) and a wide range of pH (from 1 to 14). As an application example, we fabricate a two-color binary microbarcode based on SE-UCNP via a low-cost transfer printing process. Under near-infrared irradiation, the binary sequences in our barcode are readable enough to identify objects using a mobile phone camera. The hybridization of UCNPs with a siloxane matrix provides the capacity for highly stable UCNP-based applications in real environments.

Redox enzymes are industrially important for catalyzing highly complex reactions because of their excellent regio- and stereo-selectivity; however, broad application of redox enzymes has been often limited by the requirement of stoichiometric supply of cofactors such as β-nicotinamide adenine dinucleotide (NADH). Here, we report light-driven cofactor regeneration coupled with water oxidation by employing a photoelectrochemical cell platform consisted of a FeOOH/Fe2O3 photoanode and a black silicon photocathode. The FeOOH layer deposited on Fe2O3 surface decreased reaction barriers for water oxidation. The black silicon photocathode exhibited high photocurrent response and superior capacity to drive cofactor reduction. The cofactor regeneration yield in the photoelectrochemical cell was almost two-fold higher than that obtained in homogenous system, which demonstrates that photoelectrochemical cell is a promising platform for redox biocatalytic reactions using water as an electron donor.

We present the photoelectrochemical (PEC) regeneration of nicotinamide cofactors (NADH) coupled with the enzymatic synthesis of formate from CO2 towards mimicking natural photosynthesis. The water oxidation-driven PEC platform exhibited high yield and the rate of NADH regeneration was compared to many other homogeneous, photochemical systems. We successfully coupled solar-assisted NADH reduction with enzymatic CO2 reduction to formate under continuous CO2 injection.

Peptide self-assembly is a facile route to the development of bioorganic hybrid materials that have sophisticated nanostructures toward diverse applications. Here, we report the synthesis of self-assembled peptide (Fmoc-diphenylalanine, Fmoc-FF)/graphitic carbon nitride (g-C3N4) hydrogels for light harvesting and biomimetic photosynthesis through noncovalent interactions between aromatic rings in Fmoc-FF nanofibers and tris-s-triazine in g-C3N4 nanosheets. According to our analysis, the photocurrent density of the Fmoc-FF/g-C3N4 hydrogel was 1.8× higher (0.82 μA cm–1) than that of the pristine g-C3N4. This is attributed to effective exfoliation of g-C3N4 nanosheets in the Fmoc-FF/g-C3N4 network, facilitating photoinduced electron transfers. The Fmoc-FF/g-C3N4 hydrogel reduced NAD+ to enzymatically active NADH under light illumination at a high rate of 0.130 mol g–1 h–1 and drove light-responsive redox biocatalysis. Moreover, the Fmoc-FF/g-C3N4 scaffold could well-encapsulate key photosynthetic components,...

Artificial photosynthesis in nanobiocatalytic assemblies aims to reconstruct man-made photosensitizers, electron mediators, electron donors, and redox enzymes for solar synthesis of valuable chemicals through photochemical cofactor regeneration. Herein, we report, for the first time, on nanobiocatalytic artificial photosynthesis in near-infrared (NIR) light, which constitutes over 46% of the solar energy. For NIR-light-driven photoenzymatic synthesis, we synthesized silica-coated upconversion nanoparticles, Si-NaYF4:Yb,Er and Si-NaYF4:Yb,Tm, for efficient photon-conversion through Förster resonance energy transfer (FRET) with rose bengal (RB), a photosensitizer. We observed NIR-induced electron transfer by using linear sweep voltammetric analysis; this indicates that photoexcited electrons of RB/Si-NaYF4:Yb,Er are transferred to NAD+ through a Rh-based electron mediator. RB/Si-NaYF4:Yb,Er nanoparticles, which exhibit higher FRET efficiency due to more spectral overlap than RB/Si-NaYF4:Yb,Tm, perform much better in the photoenzymatic conversion.

We report on a silicon-based photoelectrochemical cell that integrates a formate dehydrogenase from Thiobacillus sp. (TsFDH) to convert CO2 to formate using water as an electron donor under visible light irradiation and an applied bias. Our current study suggests that the deliberate integration of biocatalysis to a light-harvesting platform could provide an opportunity to synthesize valuable chemicals with the use of earth-abundant materials and sustainable resources.