Lignin is the most abundant renewable and sustainable source of aromatic compounds to replace fossil resources, causing environmental issues. However, most lignin generated from pulping and biorefinery processes is combusted or discarded as waste. In this work, we first propose a photocatalytic artificial wood platform consisting of lignin and cellulose, inspired by woody cell walls, where lignin is arranged around cellulose fibers. The wood-mimetic particles were fabricated through reconstitution after the complete dissolution of lignin and cellulose. Intensive characterization revealed that the introduction of cellulose suppressed lignin’s self-aggregation, which limits its practical photocatalytic applications. As a result, the artificial wood photocatalyst exhibited a 3.2 times higher production rate of H2O2 from oxygen and water than lignin under solar light. The wood-mimetic photocatalyst was further coupled with an unspecific peroxygenase (UPO) biocatalyst to catalyze the selective oxygenation of inert C–H bonds using H2O2 as an oxidant. The wood-UPO hybrid catalyst demonstrated a universal photobiocatalytic oxyfunctionalization of various hydrocarbons with a higher total turnover number and turnover frequency than the lignin-UPO catalyst. This work suggests a practical strategy to utilize waste lignin as a photocatalyst and further demonstrates sustainable biosolar oxygenation reactions using sunlight and water as green energy and electron sources, respectively.@en

Solar-driven N₂ fixation offers a green alternative to the highly energy-intensive Haber-Bosch process that releases more than 300 million metric tons of CO₂ annually to form NH₃. However, N₂-reducing photoelectrochemical (PEC) studies have not elucidated how an oxidation reaction affects the N₂ reduction reaction (NRR). Here, we report a bias-free PEC platform for N₂ reduction to NH₃ and H₂O oxidation to O₂ and H₂O₂. Under solar light, the molybdenum-doped bismuth vanadate-based photoanodes extract electrons from H₂O and transfer them to the silicon photovoltaic-wired hematite photocathode. The light-absorbing cathode receives the electrons to drive the NRR, which is influenced by the H₂O oxidation reaction's conditions. Furthermore, the integration of PEC NRR with H₂O₂-dependent biocatalytic oxyfunctionalization achieves simultaneous synthesis of valuable chemicals on both electrodes. This work presents the first example of a PEC NRR platform coupled with H₂O oxidation and H₂O₂-dependent oxygenation for unbiased chemical synthesis using N₂, H₂O, and sunlight.

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The pulp and paper manufacturers generate approximately 50 million metric tons of lignin per annum, most of which has been abandoned or incinerated because of lignin's recalcitrant nature. Here, we report bias-free photoelectrochemical (PEC) oxidation of lignin coupled with asymmetric hydrogenation of C=C bonds. The PEC platform consists of a hematite (α-Fe2O3) photoanode and a silicon photovoltaic-wired mesoporous indium tin oxide (Si/mesoITO) photocathode. We substantiate a new function of photoelectroactivated α-Fe2O3 to extract electrons from lignin. The extracted electrons are transferred to the Si/mesoITO photocathode for regenerating synthetic nicotinamide cofactor analogues (mNADHs). We demonstrate that the reduction kinetics of mNAD+s depend on their reduction peak potentials. The regenerated mNADHs activate ene-reductases from the old yellow enzyme (OYE) family, which catalyze enantioselective reduction of α,β-unsaturated hydrocarbons. This lignin-fueled biocatalytic PEC system exhibits an excellent OYE's turnover frequency and total turnover number for photobiocatalytic trans-hydrogenation through cofactor regeneration. This work presents the first example of PEC regeneration of mNADHs and opens up a sustainable route for bias-free chemical synthesis using renewable lignin waste as an electron feedstock.

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Enzymes are the catalyst of choice for highly selective reactions, offering nature-inspired approaches for sustainable chemical synthesis. Oxidative enzymes (e.g., monooxygenases, peroxygenases, oxidases, or dehydrogenases) catalyze a variety of enantioselective oxyfunctionalization and dehydrogenation reactions under mild conditions. To sustain the catalytic cycles of these enzymes, constant supply with or withdrawal of reducing equivalents (electrons) is required. Being redox by nature, photocatalysis appears a ‘natural choice’ to accomplish the electron-relay role, and many photoenzymatic oxidation reactions have been developed in the past years. In this contribution, we critically summarize the current developments in photoredoxbiocatalysis, highlight some promising concepts but also discuss the current limitations.

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Heat is a fundamental feedstock, where more than 80% of global energy comes from fossil-based heating process. However, it is mostly wasted due to a lack of proper techniques of utilizing the low-quality waste heat (<100 °C). Here we report thermoelectrobiocatalytic chemical conversion systems for heat-fueled, enzyme-catalyzed oxyfunctionalization reactions. Thermoelectric bismuth telluride (Bi₂Te₃) directly converts low-temperature waste heat into chemical energy in the form of H₂O₂ near room temperature. The streamlined reaction scheme (e.g., water, heat, enzyme, and thermoelectric material) promotes enantio- and chemo-selective hydroxylation and epoxidation of representative substrates (e.g., ethylbenzene, propylbenzene, tetralin, cyclohexane, cis-β-methylstyrene), achieving a maximum total turnover number of rAaeUPO (TTN_rAaeUPO) over 32000. Direct conversion of vehicle exhaust heat into the enantiopure enzymatic product with a rate of 231.4 μM h⁻¹ during urban driving envisions the practical feasibility of thermoelectrobiocatalysis.

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Peroxygenases have long inspired the selective oxyfunctionalization of various aliphatic and aromatic compounds, because of their broad substrate spectrum and simplicity of catalytic mechanism. This study provides a proof-of-concept of piezobiocatalysis by demonstrating peroxygenase-catalyzed oxyfunctionalization reactions fueled by piezocatalytically generated H₂O₂. Bismuth oxychloride (BiOCl) generated H₂O₂ in situ via an oxygen reduction reaction under ultrasonic wave conditions. Through the simple combination of water, ultrasound, recombinant, evolved unspecific peroxygenase from Agrocybe aegerita (rAaeUPO), and BiOCl, the piezobiocatalytic platform accelerated selective hydroxylation of ethylbenzene to enantiopure (R)-1-phenylethanol [total turnover number of rAaeUPO (TTN_rAaeUPO), 2002; turnover frequency, 77.7 min^-1 >99% enantiomeric excess (ee)]. The BiOCl-rAaeUPO couple also catalyzed other representative substrates (e.g., propylbenzene, 1-chloro-4-ethylbenzene, cyclohexane, and cis-β-methylstyrene) with high turnover frequency and selectivity. We alleviated the oxidative stress of piezocatalytically generated OH^- on rAaeUPO by spatial separation of rAaeUPO and BiOCl, which resulted in greatly enhanced TTN_rAaeUPO of >3900 and the notable prolongation of reaction time. Overall, the BiOCl-rAaeUPO couple serves as a mechanical-to-chemical energy conversion platform for driving peroxygenase-catalyzed reactions under ultrasonic conditions.

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Inspired by natural photosynthesis, biocatalytic photoelectrochemical (PEC) platforms are gaining prominence for the conversion of solar energy into useful chemicals by combining redox biocatalysis and photoelectrocatalysis. Herein, we report a dual biocatalytic PEC platform consisting of a molybdenum (Mo)-doped BiVO₄ (Mo:BiVO₄) photoanode and an inverse opal ITO (IO-ITO) cathode that gives rise to the coupling of peroxygenase and ene-reductase-mediated catalysis, respectively. In the PEC cell, the photoexcited electrons generated from the Mo:BiVO₄ are transferred to the IO-ITO and regenerate reduced flavin mononucleotides to drive ene-reductase-catalyzed trans-hydrogenation of ketoisophrone to (R)-levodione. Meanwhile, the photoactivated Mo:BiVO₄ evolves H₂O₂ in situ via a two-electron water-oxidation process with the aid of an applied bias, which simultaneously supplies peroxygenases to drive selective hydroxylation of ethylbenzene into enantiopure (R)-1-phenyl-1-hydroxyethane. Thus, the deliberate integration of PEC systems with redox biocatalytic reactions can simultaneously produce valuable chemicals on both electrodes using solar-powered electrons and water.

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The use of neat reaction media, that is the avoidance of additional solvents, is the simplest and the most efficient approach to follow in biocatalysis. Here, we show that unspecific peroxygenase from Agrocybe aegerita (AaeUPO) can hydroxylate the neat model substrate cyclohexane. H₂O₂ was photocatalytically generated in situ by nitrogen-doped carbon nanodots (N−CNDs) and UV LED illumination. AaeUPO entrapment in alginate beads increased enzyme stability and facilitated the reaction in neat cyclohexane. N−CNDs absorption in beads containing AaeUPO created a 2-in-1 heterogeneous photobiocatalyst that was active for up to seven days under reaction conditions and produced cyclohexanol, 2.5 mM. To increase productivity, the bead size and the photocatalyst-to-enzyme ratio have been identified as promising targets for optimisation.

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Although our knowledge of climate change impacts on energy systems has increased substantially over the past few decades, there remains a lack of comprehensive overview of impacts across spatial scales. Here, we analyse results of 220 studies projecting climate impacts on energy systems globally and at the regional scale. Globally, a potential increase in cooling demand and decrease in heating demand can be anticipated, in contrast to slight decreases in hydropower and thermal energy capacity. Impacts at the regional scale are more mixed and relatively uncertain across regions, but strongest impacts are reported for South Asia and Latin America. Our assessment shows that climate impacts on energy systems at regional and global scales are uncertain due partly to the wide range of methods and non-harmonized datasets used. For a comprehensive assessment of climate impacts on energy, we propose a consistent multi-model assessment framework to support regional-to-global-scale energy planning.

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Peroxygenases are very interesting catalysts for specific oxyfunctionalization chemistry. Instead of relying on complicated electron transport chains, they rely on simple hydrogen peroxide as the stoichiometric oxidant. Their poor robustness against H₂O₂ can be addressed via in situ generation of H₂O₂. Here we report that simple graphitic carbon nitride (g-C₃N₄) is a promising photocatalyst to drive peroxygenase-catalyzed hydroxylation reactions. The system has been characterized by outlining not only its scope but also its current limitations. In particular, spatial separation of the photocatalyst from the enzyme is shown as a solution to circumvent the undesired inactivation of the biocatalyst. Overall, very promising turnover numbers of the biocatalyst of more than 60.000 have been achieved.

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Nicotinamide adenine dinucleotide (NAD⁺) is a key redox compound in all living cells responsible for energy transduction, genomic integrity, life-span extension, and neuromodulation. Here, we report a new function of NAD⁺ as a molecular photocatalyst in addition to the biological roles. Our spectroscopic and electrochemical analyses reveal light absorption and electronic properties of two p-conjugated systems of NAD⁺. Furthermore, NAD⁺ exhibits a robust photostability under UV-Vis-NIR irradiation. We demonstrate photocatalytic redox reactions driven by NAD⁺, such as O₂ reduction, H₂O oxidation, and the formation of metallic nanoparticles. Beyond the traditional role of NAD⁺ as a cofactor in redox biocatalysis, NAD⁺ executes direct photoactivation of oxidoreductases through the reduction of enzyme prosthetic groups. Consequently, the synergetic integration of biocatalysis and photocatalysis using NAD⁺ enables solar-to-chemical conversion with the highest-ever-recorded turnover frequency and total turnover number of 1263.4 hour⁻¹ and 1692.3, respectively, for light-driven biocatalytic trans-hydrogenation.

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Peroxygenases catalyze selective oxyfunctionalization of hydrocarbons with high conversion efficiencies using H₂O₂ as a key cosubstrate. Here, we report an unbiased photoelectrochemical (PEC) tandem structure consisting of a FeOOH/BiVO₄ photoanode, a Cu(In,Ga)Se₂ solar absorber, and a graphitic carbon nitride/reduced graphene oxide hybrid cathode for light-driven peroxygenase catalysis. Powered by sufficient photovoltage generated by the solar absorber, the PEC platform generates H₂O₂ in situ through reductive activation of molecular oxygen using water as an electron donor in the absence of external bias. The peroxygenase from Agrocybe aegerita catalyzed the stereoselective hydroxylation of ethylbenzene to (R)-1-phenylethanol with total turnover numbers over 43 300 and high enantioselectivity (ee > 99%) in the unbiased PEC tandem system.

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Peroxygenases require a controlled supply of H₂O₂ to operate efficiently. Here, we propose a photocatalytic system for the reductive activation of ambient O₂ to produce H₂O₂ which uses the energy provided by visible light more efficiently based on the combination of wavelength-complementary photosensitizers. This approach was coupled to an enzymatic system to make formate available as a sacrificial electron donor. The scope and current limitations of this approach are reported and discussed.

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We report visible light-driven, asymmetric hydrogenation of C=C bonds using an ene-reductase from Thermus scotoductus SA-01 (TsOYE) and a light-harvesting dye (rose bengal, RB) co-immobilized in an alginate hydrogel. Highly efficient encapsulation of RB in alginate hydrogel was achieved using the intrinsic affinity between TsOYE and RB, which allowed for the construction of robust RB-TsOYE-loaded alginate capsules. In the absence of NADH, the photobiocatalytic system facilitated asymmetric reduction of 2-methylcyclohexenone to an enantiopure (R)-2-methylcyclohexanone (ee > 99%; max. conversion, 70.4%; turnover frequency, 1.54 min ^-1 turnover number, 300.2) under illumination. A series of stability tests revealed a significant enhancement of TsOYE's robustness in alginate hydrogel against heat and chemical denaturants. This study provides insight into a greener and sustainable approach of cofactor-free OYE catalysis for producing value-added chemicals using light energy.

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Light-driven activation of redox enzymes is an emerging route for sustainable chemical synthesis. Among redox enzymes, the family of Old Yellow Enzyme (OYE) dependent on the nicotinamide adenine dinucleotide cofactor (NADH) catalyzes the stereoselective reduction of α,β-unsaturated hydrocarbons. Here, we report OYE-catalyzed asymmetric hydrogenation through light-driven regeneration of NADH and its analogues (mNADHs) by N-doped carbon nanodots (N-CDs), a zero-dimensional photocatalyst. Our spectroscopic and photoelectrochemical analyses verified the transfer of photo-induced electrons from N-CDs to an organometallic electron mediator (M) for highly regioselective regeneration of cofactors. Light triggered the reduction of NAD⁺ and mNAD⁺s with the cooperation of N-CDs and M, and the reduction behaviors of cofactors were dependent on their own reduction peak potentials. The regenerated cofactors subsequently delivered hydrides to OYE for stereoselective conversions of a broad range of substrates with excellent biocatalytic efficiencies.

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Peroxygenases are very promising catalysts for oxyfunctionalization reactions. Their practical applicability, however, is hampered by their sensitivity against the oxidant (H₂O₂), therefore necessitating in situ generation of H₂O₂. Here, we report a photoelectrochemical approach to provide peroxygenases with suitable amounts of H₂O₂ while reducing the electrochemical overpotential needed for the reduction of molecular oxygen to H₂O₂. When tethered on single-walled carbon nanotubes (SWNTs) under illumination, flavins allowed for a marked anodic shift of the oxygen reduction potential in comparison to pristine SWNT and/or nonilluminated electrodes. This flavin-SWNT-based photoelectrochemical platform enabled peroxygenases-catalyzed, selective hydroxylation reactions.

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In green plants, solar-powered electrons are transferred through sophistically arranged photosystems and are subsequently channelled into the Calvin cycle to generate chemical energy. Inspired by the natural photosynthetic scheme, a photoelectrochemical cell (PEC) is constructed configured with protonated graphitic carbon nitride (p-g-C₃N₄) and carbon nanotube hybrid (CNT/p-g-C₃N₄) film cathode, and FeOOH-deposited bismuth vanadate (FeOOH/BiVO₄) photoanode for the production of industrially useful chiral alkanes using an old yellow enzyme homologue from Thermus scotoductus (TsOYE). In the biocatalytic PEC platform, photoexcited electrons provided by the FeOOH/BiVO₄ photoanode are transferred to the robust and self-standing CNT/p-g-C₃N₄ hybrid film that electrocatalytically reduces flavin mononucleotide (FMN) mediator. The p-g-C₃N₄ promotes a two-electron reduction of FMN coupled with an accelerated electron transfer by the conductive CNT network. The reduced FMN subsequently delivers the electrons to TsOYE for the highly enantioselective conversion of ketoisophorone to (R)-levodione. Under light illumination (>420 nm) and external bias, (R)-levodione is synthesized with the enantiomeric excess value of above 83%, not influenced by the scale of applied bias, simultaneously exhibiting stable and high current efficiency. The results suggest that the biocatalytic PEC made up of economical materials can selectively synthesize high-value organic chemicals using water as an electron donor.

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Enoate reductases from the family of old yellow enzymes (OYEs) can catalyze stereoselective trans-hydrogenation of activated C=C bonds. Their application is limited by the necessity for a continuous supply of redox equivalents such as nicotinamide cofactors [NAD(P)H]. Visible light-driven activation of OYEs through NAD(P)H-free, direct transfer of photoexcited electrons from xanthene dyes to the prosthetic flavin moiety is reported. Spectroscopic and electrochemical analyses verified spontaneous association of rose bengal and its derivatives with OYEs. Illumination of a white light-emitting-diode triggered photoreduction of OYEs by xanthene dyes, which facilitated the enantioselective reduction of C=C bonds in the absence of NADH. The photoenzymatic conversion of 2-methylcyclohexenone resulted in enantiopure (ee>99 %) (R)-2-methylcyclohexanone with conversion yields as high as 80–90 %. The turnover frequency was significantly affected by the substitution of halogen atoms in xanthene dyes.

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