Single-atom nickel terminating sp2 and sp3 nitride in polymeric carbon nitride for visible-light photocatalytic overall water splitting

Polymeric carbon nitride (PCN) has been widely used as a metal-free photocatalyst for solar hydrogen generation from water. However, rapid charge carrier recombination and sluggish water catalysis kinetics have greatly limited its photocatalytic performance for overall water splitting. Herein, a single-atom Ni terminating agent was introduced to coordinate with the heptazine units of PCN to create new hybrid orbitals. Both theoretical calculation and experimental evidence revealed that the new hybrid orbitals synergistically broadened visible light absorption via a metal-to-ligand charge transfer (MLCT) process, and accelerated the separation and transfer of photoexcited electrons and holes. The obtained single-atom Ni terminated PCN (PCNNi), without an additional cocatalyst loading, realized efficient photocatalytic overall water splitting into easily-separated gas-product H₂ and liquid-product H₂O₂ under visible light, with evolution rates reaching 26.6 and 24.0 μmol g⁻¹ h⁻¹, respectively. It was indicated that single-atom Ni and the neighboring C atom served as water oxidation and reduction active sites, respectively, for overall water splitting via a two-electron reaction pathway.

Single-atom Ni terminating agent is introduced to coordinate with sp² or sp³ N atoms in the heptazine units of PCN, realizing visible-light photocatalytic overall water splitting to H₂O₂ and H₂ without additional cocatalyst.     

Symmetry-breaking synthesis of Janus Au/CeO2 nanostructures for visible-light nitrogen photofixation

Precise manipulation of the reactive site spatial distribution in plasmonic metal/semiconductor photocatalysts is crucial to their photocatalytic performance, but the construction of Janus nanostructures through symmetry-breaking synthesis remains a significant challenge. Here we demonstrate a synthetic strategy for the selective growth of a CeO₂ semi-shell on Au nanospheres (NSs) to fabricate Janus Au NS/CeO₂ nanostructures with the assistance of a SiO₂ hard template and autoredox reaction between Ag⁺ ions and a ceria precursor. The obtained Janus nanostructures possess a spatially separated architecture and exhibit excellent photocatalytic performance toward N₂ photofixation under visible-light illumination. In this scenario, N₂ molecules are reduced by hot electrons on the CeO₂ semi-shell, while hole scavengers are consumed by hot holes on the exposed Au NS surface, greatly promoting the charge carrier separation. Moreover, the exposed Au NS surface in the Janus structures offers an additional opportunity for the fabrication of ternary Janus noble metal/Au NS/CeO₂ nanostructures. This work highlights the genuine superiority of the spatially separated nanoarchitectures in the photocatalytic reaction, offering instructive guidance for the design and construction of novel plasmonic photocatalysts.

We demonstrate a synthetic strategy to selectively grow a CeO₂ semi-shell on Au nanospheres through the symmetry-breaking synthesis. The asymmetric nanostructures facilitate the charge carrier separation during the visible-light N₂ photofixation.     

Merging the Norrish type I reaction and transition metal catalysis: photo- and Rh-promoted borylation of C–C σ-bonds of aryl ketones

Synthesis of arylboronates via borylation of C–C σ-bonds of aryl ketones was achieved by the combined use of photoenergy and a Rh catalyst. The cooperative system enables α-cleavage of photoexcited ketones to generate aroyl radicals via the Norrish type I reaction, which are successively decarbonylated and borylated with the rhodium catalyst. This work establishes a new catalytic cycle merging the Norrish type I reaction and Rh catalysis and demonstrates the new synthetic utility of aryl ketones as aryl sources for intermolecular arylation reactions.

Synthesis of arylboronates via borylation of C–C σ-bonds of aryl ketones was achieved by the combined use of photoenergy and a Rh catalyst.     

Design and synthesis of TiO2/C nanosheets with a directional cascade carrier transfer

Directed transfer of carriers, akin to excited charges in photosynthesis, in semiconductors by structural design is challenging. Here, TiO₂ nanosheets with interlayered sp² carbon and titanium vacancies are obtained by low-temperature controlled oxidation calcination. The directed transfer of carriers from the excited position to Ti-vacancies to interlayered carbon is investigated and proven to greatly increase the charge transport efficiency. The TiO₂/C obtained demonstrates excellent photocatalytic and photoelectrochemical activity and significant lithium/sodium ion storage performance. Further theoretical calculations reveal that the directional excited position/Ti-vacancies/interlayered carbon facilitate the spatial inside-out cascade electron transfer, resulting in high charge transfer kinetics.

Directional charge transfer in TiO₂ nanosheets is achieved by design of TiO₂ lattice-Ti vacancy-interlayered sp² carbon at the interface.     

Unleashing non-conjugated polymers as charge relay mediators

The core factors affecting the efficiency of photocatalysis are predominantly centered on controllable modulation of anisotropic spatial charge separation/transfer and regulating vectorial charge transport pathways in photoredox catalysis, yet it still meets with limited success. Herein, we first conceptually demonstrate the rational design of unidirectional cascade charge transfer channels over transition metal chalcogenide nanosheets (TMC NSs: ZnIn₂S₄, CdS, CdIn₂S₄, and In₂S₃), which is synergistically enabled by a solid-state non-conjugated polymer, i.e., poly(diallyldimethyl ammonium chloride) (PDDA), and MXene quantum dots (MQDs). In such elaborately designed photosystems, an ultrathin PDDA layer functions as an intermediate charge transport mediator to relay the directional electron transfer from TMC NSs to MQDs that serve as the ultimate electron traps, resulting in a considerably boosted charge separation/migration efficiency. The suitable energy level alignment between TMC NSs and MQDs, concurrent electron-withdrawing capabilities of the ultrathin PDDA interim layer and MQDs, and the charge transport cascade endow the self-assembled TMC/PDDA/MQD heterostructured photosystems with conspicuously improved photoactivities toward anaerobic selective reduction of nitroaromatics to amino derivatives and photocatalytic hydrogen evolution under visible light irradiation. Furthermore, we ascertain that this concept of constructing a charge transfer cascade in such TMC-insulating polymer-MQD photosystems is universal. Our work would afford novel insights into smart design of spatial vectorial charge transport pathways by precise interface modulation via non-conjugated polymers for solar energy conversion.

Electron relay of interim polymer layer boosts photocatalytic organic transformation.     

Conductivity and photoconductivity in a two-dimensional zinc bis(triarylamine) coordination polymer

We report the synthesis and characterization of a 2D semiconductive and photoconductive coordination polymer. [Zn(TPPB)(Cl₂)]·H₂O (1) (TPPB = N¹,N¹,N⁴,N⁴-tetrakis(4-(pyridin-4-yl)phenyl)benzene-1,4-diamine) consists of a TPPB redox-active linker with bis(triarylamine) as the core. It consists of two redox sites connected with a benzene ring as a bridge. Thus, this forms an extended conjugation pathway when the TPPB ligand is coordinated with the Zn²⁺ metal ions. The single crystal conductivity measurement revealed conductivity of 1 to be in the range of 0.83 to 1.9 S cm⁻¹. Band structure analysis predicted that 1 is a semiconductor from the delocalization of electronic transport in the network. The computational calculations show the difference in charge distribution between holes and electrons, which led to spatial separation. This implies a long charge carrier lifetime as indicated by lifetime measurement. Incorporating a bis(triarylamine)-based redox-active linker could lead to a new semiconductive scaffold material with photocatalytic applications.

This work highlights the importance of bis(triarylamine) redox-active linker in promoting the semiconductive and photoconductive behavior of a 2D zinc-based coordination polymer.     

An organophotocatalytic late-stage N–CH3 oxidation of trialkylamines to N-formamides with O2 in continuous flow

We report an organophotocatalytic, N–CH₃-selective oxidation of trialkylamines in continuous flow. Based on the 9,10-dicyanoanthracene (DCA) core, a new catalyst (DCAS) was designed with solubilizing groups for flow processing. This allowed O₂ to be harnessed as a sustainable oxidant for late-stage photocatalytic N–CH₃ oxidations of complex natural products and active pharmaceutical ingredients bearing functional groups not tolerated by previous methods. The organophotocatalytic gas–liquid flow process affords cleaner reactions than in batch mode, in short residence times of 13.5 min and productivities of up to 0.65 g per day. Spectroscopic and computational mechanistic studies showed that catalyst derivatization not only enhanced solubility of the new catalyst compared to poorly-soluble DCA, but profoundly diverted the photocatalytic mechanism from singlet electron transfer (SET) reductive quenching with amines toward energy transfer (E_nT) with O₂.

An N–CH₃-selective trialkylamine oxidation to N-formamides is reported in continuous flow using gaseous O₂. A novel, enhanced-solubility dicyanoanthracene organophotocatalyst switched the photochemical mechanism from electron to energy transfer.     

MnO2 nanosheets as a carrier and accelerator for improved live-cell biosensing application of CRISPR/Cas12a

Besides gene-editing, the CRISPR/Cas12a system has also been widely used in in vitro biosensing, but its applications in live-cell biosensing are rare. One reason is lacking appropriate carriers to synchronously deliver all components of the CRISPR/Cas12a system into living cells. Herein, we demonstrate that MnO₂ nanosheets are an excellent carrier of CRISPR/Cas12a due to the two important roles played by them. Through a simple mixing operation, all components of the CRISPR/Cas12a system can be loaded on MnO₂ nanosheets and thus synchronously delivered into cells. Intracellular glutathione (GSH)-induced decomposition of MnO₂ nanosheets not only results in the rapid release of the CRISPR/Cas12a system in cells but also provides Mn²⁺ as an accelerator to promote CRISPR/Cas12a-based biosensing of intracellular targets. Due to the merits of highly efficient delivery, rapid intracellular release, and the accelerated signal output reaction, MnO₂ nanosheets work better than commercial liposome carriers in live-cell biosensing analysis of survivin messenger RNA (mRNA), producing much brighter fluorescence images in a shorter time. The use of MnO₂ nanosheets might provide a good carrier for different CRISPR/Cas systems and achieve the rapid and sensitive live-cell biosensing analysis of different intracellular targets, thus paving a promising way to promote the applications of CRISPR/Cas systems in living cells.

Herein, we demonstrate that MnO₂ nanosheets are an excellent carrier of CRISPR/Cas12a due to the two important roles played by them.     

Bridging electrocatalyst and cocatalyst studies for solar hydrogen production via water splitting

Solar-driven water-splitting has been considered as a promising technology for large-scale generation of sustainable energy for succeeding generations. Recent intensive efforts have led to the discovery of advanced multi-element-compound water-splitting electrocatalysts with very small overpotentials in anticipation of their application to solar cell-assisted water electrolysis. Although photocatalytic and photoelectrochemical water-splitting systems are more attractive approaches for scaling up without much technical complexity and high investment costs, improving their efficiencies remains a huge challenge. Hybridizing photocatalysts or photoelectrodes with cocatalysts has been an effective scheme to enhance their overall solar energy conversion efficiencies. However, direct integration of highly-active electrocatalysts as cocatalysts introduces critical factors that require careful consideration. These additional requirements limit the design principle for cocatalysts compared with electrocatalysts, decelerating development of cocatalyst materials. This perspective first summarizes the recent advances in electrocatalyst materials and the effective strategies to assemble cocatalyst/photoactive semiconductor composites, and further discusses the core principles and tools that hold the key in designing advanced cocatalysts and generating a deeper understanding on how to further push the limits of water-splitting efficiency.

This perspective briefly reviews recently developed water splitting electrocatalyst materials and discusses their utilization as cocatalysts for photocatalytic and photoelectrochemical water splitting systems.     

Controlling transmembrane ion transport via photo-regulated carrier mobility

Stimuli-responsive transmembrane ion carriers allow for targeted and controllable transport activity, with potential applications as therapeutics for channelopathies and cancer, and in fundamental studies into ion transport phenomena. These applications require OFF–ON activation from a fully inactive state which does not exhibit background activity, but this remains challenging to achieve with synthetic transport systems. Here we introduce a novel mechanism for photo-gating mobile ion carriers, which involves modulating the mobility of the carriers within the lipid bilayer membrane. By appending a membrane-targeting anchor to the carrier using a photo-cleavable linker, the carrier''s ion transport activity is fully switched off by suppressing its ability to shuttle between the two aqueous-membrane interfaces of the bilayer. The system can be reactivated rapidly in situ within the membrane by photo-triggered cleavage of the anchor to release the mobile ion carrier. This approach does not involve direct functionalization of the ion binding site of the carrier, and so does not require the de novo design of novel ion binding motifs to implement the photo-caging of activity. This work demonstrates that controlling the mobility of artificial transport systems enables precise control over activity, opening up new avenues for spatio-temporally targeted ionophores.

Photo-gated anion transport is achieved by modulating the mobility of mobile carriers within a lipid bilayer membrane, using a photo-cleavable membrane anchor. This enables in situ, off–on activation of transport in vesicles.     

Rhodium-catalysed ortho-alkynylation of nitroarenes

The ortho-alkynylation of nitro-(hetero)arenes takes place in the presence of a Rh(iii) catalyst to deliver a wide variety of alkynylated nitroarenes regioselectively. These interesting products could be further derivatized by selective reduction of the nitro group or palladium-catalysed couplings. Experimental and computational mechanistic studies demonstrate that the reaction proceeds via a turnover-limiting electrophilic C–H metalation ortho to the strongly electron-withdrawing nitro group.

Rh(iii)-catalyzed ortho-alkynylation of nitro-(hetero)arenes leads to a wide variety of alkynylated nitroarenes via a turnover-limiting electrophilic C–H ortho-metalation.     

Rhodium diamidobenzene complexes: a tale of different substituents on the diamidobenzene ligand

Diamidobenzene ligands are a prominent class of redox-active ligands owing to their electron reservoir behaviour, as well as the possibility of tuning the steric and the electronic properties of such ligands through the substituents on the N-atoms of the ligands. In this contribution, we present Rh(iii) complexes with four differently substituted diamidobenzene ligands. By using a combination of crystallography, NMR spectroscopy, electrochemistry, UV-vis-NIR/EPR spectroelectrochemistry, and quantum chemical calculations we show that the substituents on the ligands have a profound influence on the bonding, donor, electrochemical and spectroscopic properties of the Rh complexes. We present, for the first time, design strategies for the isolation of mononuclear Rh(ii) metallates whose redox potentials span across more than 850 mV. These Rh(ii) metallates undergo typical metalloradical reactivity such as activation of O₂ and C–Cl bond activations. Additionally, we also show that the substituents on the ligands dictate the one versus two electron nature of the oxidation steps of the Rh complexes. Furthermore, the oxidative reactivity of the metal complexes with a [CH₃]⁺ source leads to the isolation of a unprecedented, homobimetallic, heterovalent complex featuring a novel π-bonded rhodio-o-diiminoquionone. Our results thus reveal several new potentials of the diamidobenzene ligand class in organometallic reactivity and small molecule activation with potential relevance for catalysis.

Diamidobenzene ligands are versatile platforms in organometallic Rh-chemistry. They allow the isolation of tunable mononuclear ate-complexes, and the formation of a unprecedented homobimetallic, heterovalent complex.     

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI₃ nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn²⁺ doping (1) enlarges the longitudinal optical (LO)–acoustic phonon bandgap, (2) enhances the electron–LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn²⁺ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier–phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron–LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Mn doping modulates the hot carrier dynamics in all-inorganic lead halide perovskite nanocrystals according to the excitation energy.     

Light-driven reduction of aromatic olefins in aqueous media catalysed by aminopyridine cobalt complexes

A catalytic system based on earth-abundant elements that efficiently hydrogenates aryl olefins using visible light as the driving-force and H₂O as the sole hydrogen atom source is reported. The catalytic system involves a robust and well-defined aminopyridine cobalt complex and a heteroleptic Cu photoredox catalyst. The system shows the reduction of styrene in aqueous media with a remarkable selectivity (>20 000) versus water reduction (WR). Reactivity and mechanistic studies support the formation of a [Co–H] intermediate, which reacts with the olefin via a hydrogen atom transfer (HAT). Synthetically useful deuterium-labelled compounds can be straightforwardly obtained by replacing H₂O with D₂O. Moreover, the dual photocatalytic system and the photocatalytic conditions can be rationally designed to tune the selectivity for aryl olefin vs. aryl ketone reduction; not only by changing the structural and electronic properties of the cobalt catalysts, but also by modifying the reduction properties of the photoredox catalyst.

A dual catalytic system based on earth-abundant elements reduces aryl olefins to alkanes in aqueous media under visible light. Mechanistic studies allow for rational tunning of the system for the selective reduction of aryl olefins vs ketones and vice versa.     

Selective photocatalytic aerobic oxidation of methane into carbon monoxide over Ag/AgCl@SiO2

Design of active catalysts for chemical utilization of methane under mild conditions is of great importance, but remains a challenging task. Here, we prepared a Ag/AgCl with SiO₂ coating (Ag/AgCl@SiO₂) photocatalyst for methane oxidation to carbon monoxide. High carbon monoxide production (2.3 μmol h⁻¹) and high selectivity (73%) were achieved. SiO₂ plays a key role in the superior performance by increasing the lifetime of the photogenerated charge carriers. Based on a set of semi in situ infrared spectroscopy, electron paramagnetic resonance, and electronic property characterization studies, it is revealed that CH₄ is effectively and selectively oxidized to CO by the in situ formation of singlet ¹O₂via the key intermediate of COOH*. Further study showed that the Ag/AgCl@SiO₂ catalyst could also drive valuable conversion using real sunlight under ambient conditions. As far we know, this is the first work on the application of SiO₂ modified Ag/AgCl in the methane oxidation reaction.

The Ag/AgCl@SiO₂ catalyst exhibits excellent photocatalytic activity in selective aerobic oxidation of methane to carbon monoxide with high selectivity, and extended real light simulation feasibility shows potential in practical application.     

Switchable photocatalysis for the chemodivergent benzylation of 4-cyanopyridines

We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides. The judicious choice of different photocatalyst quenchers allowed us to select at will between mechanistically divergent processes. The two reaction manifolds, an ipso-substitution path proceeding via radical coupling and a Minisci-type addition, enabled selective access to regioisomeric C4 or C2 benzylated pyridines, respectively. Mechanistic investigations shed light on the origin of the chemoselectivity switch.

We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides.     

Rh(i)-catalyzed dimerization of ene-vinylidenecyclopropanes for the construction of spiro[4,5]decanes and mechanistic studies

Rh(i) complex catalyzed dimerization of ene-vinylidenecyclopropanes took place smoothly to construct a series of products containing spiro[4,5]decane skeletons featuring a simple operation procedure, mild reaction conditions, and good functional group tolerance. In this paper, the combination of experimental and computational studies reveals a counterion-assisted Rh(i)–Rh(iii)–Rh(v)–Rh(iii)–Rh(i) catalytic cycle involving tandem oxidative cyclometallation/reductive elimination/selective oxidative addition/selective reductive elimination/reductive elimination steps; in addition, a pentavalent spiro-rhodium intermediate is identified as the key intermediate in this dimerization reaction upon DFT calculation.

Rh(i) complex catalyzed dimerization of ene-vinylidenecyclopropanes has been demonstrated, and its reaction mechanism is revealed based on a series of mechanistic studies.     

Stereodivergent synthesis of β-iodoenol carbamates with CO2via photocatalysis

Photocatalytic conversion of carbon dioxide (CO₂) into value-added chemicals is of great significance from the viewpoint of green chemistry and sustainable development. Here, we report a stereodivergent synthesis of β-iodoenol carbamates through a photocatalytic three-component coupling of ethynylbenziodoxolones, CO₂ and amines. By choosing appropriate photocatalysts, both Z- and E-isomers of β-iodoenol carbamates, which are difficult to prepare using existing methods, can be obtained stereoselectively. This transformation featured mild conditions, excellent functional group compatibility and broad substrate scope. The potential synthetic utility of this protocol was demonstrated by late-stage modification of bioactive molecules and pharmaceuticals as well as by elaborating the products to access a wide range of valuable compounds. More importantly, this strategy could provide a general and practical method for stereodivergent construction of trisubstituted alkenes such as triarylalkenes, which represents a fascinating challenge in the field of organic chemistry research. A series of mechanism investigations revealed that the transformation might proceed through a charge-transfer complex which might be formed through a halogen bond.

Stereodivergent synthesis of β-iodoenol carbamates was achieved via a photocatalytic three-component coupling reaction of ethynylbenziodoxolones, CO₂ and amines.     

Understanding the mechanism of direct visible-light-activated [2 + 2] cycloadditions mediated by Rh and Ir photocatalysts: combined computational and spectroscopic studies

The mechanism of [2 + 2] cycloadditions activated by visible light and catalyzed by bis-cyclometalated Rh(iii) and Ir(iii) photocatalysts was investigated, combining density functional theory calculations and spectroscopic techniques. Experimental observations show that the Rh-based photocatalyst produces excellent yield and enantioselectivity whereas the Ir-photocatalyst yields racemates. Two different mechanistic features were found to compete with each other, namely the direct photoactivation of the catalyst–substrate complex and outer-sphere triplet energy transfer. Our integrated analysis suggests that the direct photocatalysis is the inner working of the Rh-catalyzed reaction, whereas the Ir catalyst serves as a triplet sensitizer that activates cycloaddition via an outer-sphere triplet excited state energy transfer mechanism.

The mechanism of [2 + 2] cycloadditions activated by visible light and catalyzed by bis-cyclometalated Rh(iii) and Ir(iii) photocatalysts was investigated, combining density functional theory calculations and spectroscopic techniques.     

CsPbBr3–CdS heterostructure: stabilizing perovskite nanocrystals for photocatalysis

The instability of cesium lead bromide (CsPbBr₃) nanocrystals (NCs) in polar solvents has hampered their use in photocatalysis. We have now succeeded in synthesizing CsPbBr₃–CdS heterostructures with improved stability and photocatalytic performance. While the CdS deposition provides solvent stability, the parent CsPbBr₃ in the heterostructure harvests photons to generate charge carriers. This heterostructure exhibits longer emission lifetime (τ_ave = 47 ns) than pristine CsPbBr₃ (τ_ave = 7 ns), indicating passivation of surface defects. We employed ethyl viologen (EV²⁺) as a probe molecule to elucidate excited state interactions and interfacial electron transfer of CsPbBr₃–CdS NCs in toluene/ethanol mixed solvent. The electron transfer rate constant as obtained from transient absorption spectroscopy was 9.5 × 10¹⁰ s⁻¹ and the quantum efficiency of ethyl viologen reduction (Φ_EV⁺˙) was found to be 8.4% under visible light excitation. The Fermi level equilibration between CsPbBr₃–CdS and EV²⁺/EV⁺˙ redox couple has allowed us to estimate the apparent conduction band energy of the heterostructure as −0.365 V vs. NHE. The insights into effective utilization of perovskite nanocrystals built around a quasi-type II heterostructures pave the way towards effective utilization in photocatalytic reduction and oxidation processes.

The insights into effective utilization of perovskite nanocrystals built around a CsPbBr₃–CdS heterostructure pave the way towards their utilization in photocatalytic reduction and oxidation processes.