Bond Scission Research Articles

Hydrophilic Poly(meth)acrylates by Controlled Radical Branching Polymerization: Hyperbranching and Fragmentation.

Topology significantly impacts polymer properties and applications. Hyperbranched polymers (HBPs) synthesized via atom transfer radical polymerization (ATRP) using inimers typically exhibit broad molecular weight distributions and limited control over branching. Alternatively, copolymerization of inibramers (IB), such as α-chloro/bromo acrylates with vinyl monomers, yields HBPs with precise and uniform branching. Herein, we described the synthesis of hydrophilic HB polyacrylates in water by copolymerizing a water-soluble IB, oligo(ethylene oxide) methyl ether 2-bromoacrylate (OEOBA), with various hydrophilic acrylate comonomers. Visible-light-mediated controlled radical branching polymerization (CRBP) with dual catalysis using eosin Y (EY) and copper complexes resulted in HBPs with various molecular weights (M n = 38 000 to 170 000) and degrees of branching (2%-24%). Furthermore, the optimized conditions enabled the successful application of the OEOBA to synthesize linear-hyperbranched block copolymers and hyperbranched polymer protein hybrids (HB-PPH), demonstrating its potential to advance the synthesis of complex macromolecular architecture under environmentally benign conditions. Copolymerization of hydrophilic methacrylate monomer, oligo(ethylene oxide) methyl ether methacrylate (OEOMA500), and inibramer OEOBA was accompanied by fragmentation via β-carbon C-C bond scission and subsequent growth of polymer chains from the fragments. Furthermore, computational studies investigating the fragmentation depending on the IB and comonomer structure supported the experimental observations. This work expands the toolkit of water-soluble inibramers for CRBP and highlights the critical influence of the inibramer structure on reaction outcomes.

A DFT-D investigation of the energetic and structural aspects of dehydrogenation of methanol on a bimetallic surface PtGe(110) exploring the germanium effect on the anti-poisoning of pt(110) catalytic activity

Platinum is the most active pure metal for dehydrogenating methanol to create hydrogen, which is crucial for fuel cells. However, one significant disadvantage that reduces the effectiveness and long-term performance of platinum catalysts is their susceptibility to CO poisoning. In the current study, we examine and elucidate the promotional impact of Ge on Pt catalysts with increased resistance to deactivation by CO poisoning. We do this by combining partial density of states calculations with electronic configuration and Mulliken atomic charges. The self-consistent periodic density functional theory with dispersion correction (DFT-D) was used to investigate the methanol adsorption and dehydrogenation mechanisms on the surface of PtGe (110). On the surface, several adsorption mechanisms of pertinent intermediates were found. Furthermore, a thorough analysis of a reaction network comprising four reaction paths revealed that, in terms of activation barriers, the first O—H bond scission of CH3OH appears to be more advantageous than C—H bond cleavage on the PtGe(110) surface. Additionally, it has been demonstrated that the main route on the PtGe(110) surface is CH3OH→CH3O→CH2O→CHO→CO evolution. The remarkable differences in the predominant reaction pathway on the Pt(110) surface, and PtGe(110) surface indicate that the Ge-doped Pt Nano catalyst is more selective and resistant to deactivation.

Mechanism study on dissociation of hydrogen and carbon dioxide towards carbon dioxide methanation

The study of carbon dioxide (CO2) methanation mechanisms widely argues on the nature and formation of intermediates. How reactants dissociate is still poorly understood. To gain deeper knowledge on its mechanism, we focused on studying reactants dissociation. After H2 dissociation and diffusion, the spillover H atom was observed, as well as the confirmation of H cluster formation on metal through aggregation by simulation and experiment. This H cluster facilitated C-O bond scission to easily form H ligand cobonded to metal, and thus resulted in high CO2 methanation performance. Four driving forces could dissociate CO2, three of them came from supports and metals, and another one was atomic H on metal as the strongest force. This simple and convenient method has wide adaptability and can be developed as an effective standard method for studying CO2 dissociation. The facile dissociation study of reactants would be very helpful in understanding the CO2 hydrogenation mechanism.

Preparation and characterization of MnIIMnIII complexes with relevance to class Ib ribonucleotide reductases

The Mn2 complex [MnII2(TPDP)(O2CPh)2](BPh4) (1, TPDP = 1,3-bis(bis(pyridin-2-ylmethyl)amino)propan-2-ol, Ph =phenyl) was prepared and subsequently characterized via single-crystal X-ray diffraction, X-ray absorption, electronic absorption, and infrared spectroscopies, and mass spectrometry. 1 was prepared in order to explore its properties as a structural and functional mimic of class Ib ribonucleotide reductases (RNRs). 1 reacted with superoxide anion (O2•–) to generate a peroxido-MnIIMnIII complex, 2. The electronic absorption and electron paramagnetic resonance (EPR) spectra of 2 were similar to previously published peroxido-MnIIMnIII species. Furthermore, X-ray near edge absorption structure (XANES) studies indicated the conversion of a MnII2 core in 1 to a MnIIMnIII state in 2. Treatment of 2 with para-toluenesulfonic acid (p-TsOH) resulted in the conversion to a new MnIIMnIII species, 3, rather than causing O—O bond scission, as previously encountered. 3 was characterized using electronic absorption, EPR, and X-ray absorption spectroscopies. Unlike other reported peroxido-MnIIMnIII species, 3 was capable of oxidative O—H activation, mirroring the generation of tyrosyl radical in class Ib RNRs, however without accessing the MnIIIMnIV state.

Interfacial high-valence Ni(IV)-enabled C-H activation for photoelectrochemical C-C bond cleavage of lignin to exclusively produce aromatic carboxylic acids

Sustainable upgrading of biomass to high-value chemicals is greatly dependent on catalytic C-C/C-O bond cleavage of high selectivity. Here, an oxidation-enhanced photoelectrochemical protocol was developed to be capable of breaking different types of C-C bonds for efficiently producing aromatic carboxylic acids (85.0–99.8% yields) from lignin. Ni local electronic state of the prepared F-Fe2O3-Co:NiOxHy with excellent durability could be modulated, and high-valence Ni(Ⅳ) reactive species played a key role in the oxidative C-C bond scission of various lignin models. In-situ characterization and control experiments indicated that photocatalytic radical and electrocatalytic interface facilitated C-H/O-H delocalization, contributing significantly to the enhanced oxidation process. In addition, quantum calculations elaborated that photo-excited holes and Ni(Ⅳ) are key reactive species for enhancive electrocatalytic cleavage of different C-C bonds in lignin to exclusively furnish aromatic carboxylic acids. This research provides a renewable funnel strategy for using solar energy to produce high-value mono-functional products from biomass.

Effect of the Activation Force of Mechanophore on Its Activation Selectivity and Efficiency in Polymer Networks.

In recent decades, more than 100 different mechanophores with a broad range of activation forces have been developed. For various applications of mechanophores in polymer materials, it is crucial to selectively activate the mechanophores with high efficiency, avoiding nonspecific bond scission of the material. In this study, we embedded cyclobutane-based mechanophore cross-linkers (I and II) with varied activation forces (fa) in the first network of the double network hydrogels and quantitively investigated the activation selectivity and efficiency of these mechanophores. Our findings revealed that cross-linker I, with a lower activation force relative to the bonds in the polymer main chain (fa-I/fa-chain = 0.8 nN/3.4 nN), achieved efficient activation with 100% selectivity. Conversely, an increase of the activation force of mechanophore II (fa-II/fa-chain = 2.5 nN/3.4 nN) led to a significant decrease of its activation efficiency, accompanied by a substantial number of nonspecific bond scission events. Furthermore, with the coexistence of two cross-linkers, significantly different activation forces resulted in the almost complete suppression of the higher-force one (i.e., I and III, fa-I/fa-III = 0.8 nN/3.4 nN), while similar activation forces led to simultaneous activations with moderate efficiencies (i.e., I and IV, fa-I/fa-IV = 0.8 nN/1.6 nN). These findings provide insights into the prevention of nonspecific bond rupture during mechanophore activation and enhance our understanding of the damage mechanism within polymer networks when using mechanophores as detectors. Besides, it establishes a principle for combining different mechanophores to design multiple mechanoresponsive functional materials.

Efficient hydrogenolysis of woody plant lignin into phenolic compounds over a CuO/CeO2 catalyst

Hydrogenolysis of lignocellulose into renewable phenolic monomers through the reductive catalytic degradation (RCD) strategy is limited by cost and applicability, and there is a need to develop effective catalysts with controlled cost and greater applicability. Herein, we report the fabrication of CuO/CeO2 catalyst toward RCD of lignocellulose for the production of monomeric phenols with different side chains. The catalyst can be adapted to softwoods (Larch and Pinus) and hardwoods (Eucalyptus and Poplar) with yields ranging from 8.8 % to 31.4 %, which afford certain monomer yields while controlling costs. Experimental results demonstrate that the acidic and basic sites of the CuO/CeO2 catalyst assist the metal sites in the depolymerization of lignin. Notably, the mechanistic investigation reveal that the methoxylation process occurs on the aliphatic hydroxyl group. Moreover, the synergistic effects of hydrogen and catalyst exhibit high hydrogenolysis activity, which contributes to the efficient C − O bond scission, thus generating the target monomer products.

Unpacking the diversity of monoterpene oxidation pathways via nitrooxy–alkyl radical ring-opening reactions and nitrooxy–alkoxyl radical bond scissions

Terrestrial vegetation emits vast quantities of monoterpenes to the atmosphere. These compounds, once oxidized, can contribute to the formation and growth of secondary organic aerosol (SOA) particles. However, studies report widely different SOA yields from atmospheric oxidation of different monoterpenes, despite their structural similarities. The NO3-radical-initiated oxidation of α-pinene for instance, leads to minimal SOA yields, whereas with Δ-carene a high SOA yield is observed. A previous study indicated that their oxidation mechanisms diverge after formation of a nitrooxy–alkoxyl radical intermediate, whose C–C bond scission reactions can either lead to early termination of the oxidative chain, thus limiting the yield of condensable vapors, or further propagate it, leading to low-volatility products. In this study, we employ computational methods to investigate these reactions in the NO3-radical oxidation of five other monoterpenes: limonene, sabinene, β-pinene, α-thujene and camphene. Additionally, we explore the possibility of rearrangement via ring-opening of the nitrooxy-alkyl radical adducts produced immediately after NO3 radical attack. Our calculations predict that alkyl radical rearrangement is dominant over O2-addition for sabinene, minor but competitive for α-thujene and β-pinene, and negligible for camphene. These rearrangements can induce further propagation of the oxidative chain, and thus higher SOA yields. Concerning alkoxyl radical C–C bond scissions, our results indicate that endocyclic nitrate species (derived from limonene and α-thujene) react preferentially via the channel leading to oxidative chain termination, whereas exocyclic nitrate species (sabinene, β-pinene, and camphene) react preferentially via channels leading to further propagation.

The impact of mechanical recycling on the degradation of polyamide

There is currently no agreement on the degradation mechanisms for PA6 as a result of mechanical recycling. In this study, PA6 was extruded five times to simulate mechanical melt recycling process. Both virgin PA6 and the extruded PA6 were characterised to determine the predominant degradation mechanism. Melt flow rate (MFR) increases with increasing number of extrusion passes suggesting a reduction in melt viscosity due to mechanical processing. Gel permeation chromatography (GPC) results confirmed a reduction in molecular weight from 18,600 g/mol to 13,100 g/mol. Chain ends titration showed a decrease in the concentration of both the amine and carboxyl chain ends after the fifth extrusion. There were no changes to the chemical structure of the virgin PA6 and extruded PA6 observed from the Fourier transform infra-red (FTIR) and Nuclear magnetic resonance (NMR) spectra. X-ray photoelectron spectroscopy (XPS) showed a reduction in the C–N peak area supporting the scission of the N-alkylamide bond. The increase in the O=C–N peak area suggests that chain recombination via branching is possible. The shorter chains have higher mobility, and this gives rise to an increase in the crystallisation rate as seen from the differential scanning calorimeter (DSC) thermograms. The appearance of the γ phase after the fifth extrusion was identified in the DSC melting endotherms. The understanding of the degradation process of recycled PA6 will enable targeted modifications involving the incorporation of additives in the recycling process to ensure good mechanical properties in the recycled polymer.

Force-controlled release of small molecules with a rotaxane actuator

Force-controlled release of small molecules offers great promise for the delivery of drugs and the release of healing or reporting agents in a medical or materials context1–3. In polymer mechanochemistry, polymers are used as actuators to stretch mechanosensitive molecules (mechanophores)4. This technique has enabled the release of molecular cargo by rearrangement, as a direct5,6 or indirect7–10 consequence of bond scission in a mechanophore, or by dissociation of cage11, supramolecular12 or metal complexes13,14, and even by ‘flex activation’15,16. However, the systems described so far are limited in the diversity and/or quantity of the molecules released per stretching event1,2. This is due to the difficulty in iteratively activating scissile mechanophores, as the actuating polymers will dissociate after the first activation. Physical encapsulation strategies can be used to deliver a larger cargo load, but these are often subject to non-specific (that is, non-mechanical) release3. Here we show that a rotaxane (an interlocked molecule in which a macrocycle is trapped on a stoppered axle) acts as an efficient actuator to trigger the release of cargo molecules appended to its axle. The release of up to five cargo molecules per rotaxane actuator was demonstrated in solution, by ultrasonication, and in bulk, by compression, achieving a release efficiency of up to 71% and 30%, respectively, which places this rotaxane device among the most efficient release systems achieved so far1. We also demonstrate the release of three representative functional molecules (a drug, a fluorescent tag and an organocatalyst), and we anticipate that a large variety of cargo molecules could be released with this device. This rotaxane actuator provides a versatile platform for various force-controlled release applications.

Leveraging Nonstrained C-C Bonds for Selective Carboacylation of an Unactivated Alkyne via Transient Dearomatization.

Carboacylation of an unsaturated bond represents a powerful transformation. However, only a few examples of carboacylation of alkyne have been reported through C-C bond scission and reconnection. Here, we report a method of carboacylation of an unactivated alkyne by utilizing nonstrained C-C bonds under gold(I) catalysis. The density functional theory computational and experimental studies reveal that the reaction proceeds through a C-to-C formal 1,3-acyl migration via a solvent cage-nested acylium cation.

Effects of radiation dose and dose rate on alginate and the use of radiation degraded alginate for peanut

Aqueous solutions of alginate (4 %) with or without hydrogen peroxide (0–2 % H2O2) were irradiated under a gamma Co-60 source. The effect of dose rate on the radiation scission yield (Gs) of resulting irradiated alginate was determined. At the dose of 20 kGy, the G(s) value of irradiated alginate decreased with the increase dose rate, suggesting that the irradiation at a suitable dose rate could further improve the radiation chemical yield of degradation. For the alginate irradiated at the same dose rate, G(s) value increased with the increase of H2O2 concentration. Average molecular weight (Mw) and polydispersity index (PI) of irradiated alginate rapidly decreased with the increase in dose and further decreased by addition of H2O2. The oligoalginate with Mw ~ 9800 g/mol was obtained by radiation degradation of 4 % alginate solution containing 2 % H2O2 at dose of 20 kGy. Radiation scission of glycoside bonds and formation of carbonyl groups (C=O) were indicated in UV and FTIR spectra of irradiated alginate. Peanut seedlings were fertilized with alginate and oligoalginate solutions, and the results showed that all growth parameters of the treated plants were better than those of the control. Furthermore, the oligoalginate prepared by gamma irradiation can be applied as a plant growth promoter for agriculture production.

An Evaluation of the Beneficial Effects of Polyamide 6's Thermal Stabilization by Ferric Chloride Complexation as a Novel Carbon Fiber Precursor

This study investigated the impact of stabilization time on pretreated polyamide 6 (PA6) fibers using various analytical techniques, including thermal analysis (TGA and DSC), infrared (IR) spectroscopy, X-ray diffraction (XRD), tensile testing, and density measurements. The two-step atmospheric air-based stabilization process for pretreated PA6 multifilament bundles involved initial thermal stabilization at 170 °C in an air atmosphere after ferric chloride impregnation, followed by a second step of thermal stabilization at 245 °C. Ferric chloride impregnation followed by thermal stabilization in an air atmosphere resulted in crucial structural transformations. The density values of the samples increased following thermal stabilization, accompanied by a decrease in tensile values. Ferric chloride pretreated and thermally stabilized PA6 fibers were found to be fully stabilized after 120 min of stabilization before the carbonization stage. The findings obtained from the DSC, XRD, and IR spectroscopy methods indicated the occurrence of disordering phases due to the scission of hydrogen bonds. The TGA findings showed significant increases in carbon yield percentages at 500 °C and 850 °C, reaching 71.4% and 63.5%, respectively, for the sample heat treated at 245 °C for 120 min. The addition of ferric chloride is expected to potentially reduce processing costs for final carbon fiber production by decreasing the time required for the thermal stabilization of PA6.

Light in a Heartbeat: Bond Scission by a Single Photon above 800 nm.

Photocages enable scientists to take full control over the activity of molecules using light as a biocompatible stimulus. Their emerging applications in photoactivated therapies call for efficient uncaging in the near-infrared (NIR) window, which represents a fundamental challenge. Here, we report synthetically accessible cyanine photocages that liberate alcohol, phenol, amine, and thiol payloads upon irradiation with NIR light up to 820 nm in aqueous media. The photocages display a unique chameleon-like behavior and operate via two distinct uncaging mechanisms: photooxidation and heterolytic bond cleavage. The latter process constitutes the first example of a direct bond scission by a single photon ever observed in cyanine dyes or at wavelengths exceeding 800 nm. Modulation of the beating rates of human cardiomyocytes that we achieved by light-actuated release of adrenergic agonist etilefrine at submicromolar concentrations and low NIR light doses (∼12 J cm-2) highlights the potential of these photocages in biology and medicine.

Methane-H2S Reforming Catalyzed by Carbon and Metal Sulfide Stabilized Sulfur Dimers.

H2S reforming of methane (HRM) provides a potential strategy to directly utilize sour natural gas for the production of COx-free H2 and sulfur chemicals. Several carbon allotropes were found to be active and selective for HRM, while the additional presence of transition metals led to further rate enhancements and outstanding stability (e.g., Ru supported on carbon black). Most metals are transformed to sulfides, but the carbon supports prevent sintering under the harsh reaction conditions. Supported by theoretical calculations, kinetic and isotopic investigations with representative catalysts showed that H2S decomposition and the recombination of surface H atoms are quasi-equilibrated, while the first C-H bond scission is the kinetically relevant step. Theory and experiments jointly establish that dynamically formed surface sulfur dimers are responsible for methane activation and catalytic turnovers on sulfide and carbon surfaces that are otherwise inert without reaction-derived active sites.

Photoinduced Cleavage of a Strained N-C Bond in an Iron Complex Supported by Super-Bulky Amidinate and Guanidinate Ligands.

The reaction of Fe2(mes)4 with the super-bulky amidines and guanidines HLAr*-R (LAr*-R = [(Ar*N)2C(R)]-, Ar* = 2,6-bis(diphenylmethyl)-4-tert-butylphenyl), R = Me (LAr*-Me), tBu (LAr*-tBu), Ph (LAr*-Ph), NiPr2 (LAr*-iPr2N), and Pip (LAr*-Pip)) gives access to the three-coordinate iron-mesityl complexes (LAr*-R)Fe(mes) only where LAr*-R = LAr*-Me, LAr*-Ph, or LAr*-Pip. Subsequent protonolysis with the N-atom transfer reagent Hdbabh (Hdbabh = 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene) is limited in success, providing in one instance a few crystals of four-coordinate (LAr*-Me)Fe(dbabh)(Hdbabh), while three-coordinate (LAr*-Pip)Fe(dbabh) is synthesized reproducibly. Complexes (LAr*-Me)Fe(dbabh)(Hdbabh) and (LAr*-Pip)Fe(dbabh) are thermally insensitive in solution to temperatures of up to 100 °C. On the other hand, both (LAr*-Me)Fe(dbabh)(Hdbabh) and (LAr*-Pip)Fe(dbabh) show sensitivity to blue LED light (395 nm), undergoing photochemical transformations. For instance, the photolysis of (LAr*-Me)Fe(dbabh)(Hdbabh) leads to N-C bond scission and C-C bond coupling across the -dbabh moieties to give four-coordinate (LAr*-Me)Fe(N=dbabh-dbabhNH2). Photolyzing pyridine-d5 (py-d5) solutions of (LAr*-Pip)Fe(dbabh) at -5 °C produces a new paramagnetic photoproduct, [P]. Due to the thermal sensitivity of compound [P], it has eluded structural characterization; yet, Evans' method measurements suggest that the iron(II) oxidation state is maintained, thereby pointing to the -dbabh moiety as the locus of chemical change. In line with this assessment, addition of excess Me3SiCl to solutions of [P] produces the iron(II) complex (LAr*-Pip)FeCl(py-d5) as shown by 1H NMR spectroscopy. Gas chromatography/mass spectrometry analysis of the solutions of [P] shows a peak in the chromatogram with a molecular mass corresponding to a formulation of C14H11N that cannot be attributed to Hdbabh. This provides evidence for the photochemical-induced isomerization of the -dbabh ligand, revealing a heretofore unknown photochemical sensitivity of this N atom transfer reagent.

Highly Selective and Efficient Perdeuteration of n‐Pentane via H/D Exchange Catalyzed by a Silica‐Supported Hafnium‐Iridium Bimetallic Complex

AbstractA Surface OrganoMetallic Chemistry (SOMC) approach is used to prepare a novel hafnium‐iridium catalyst immobilized on silica, HfIr/SiO2, featuring well‐defined [≡SiOHf(CH2tBu)2(μ‐H)3IrCp*] surface sites. Unlike the monometallic analogous materials Hf/SiO2 and Ir/SiO2, which promote n‐pentane deuterogenolysis through C−C bond scission, we demonstrate that under the same experimental conditions (1 bar D2, 250 °C, 3 h, 0.5 mol %), the heterobimetallic catalyst HfIr/SiO2 is highly efficient and selective for the perdeuteration of alkanes with D2, exemplified on n‐pentane, without substantial deuterogenolysis (<2 % at 95 % conversion). Furthermore this HfIr/SiO2 catalyst is robust and can be re‐used several times without evidence of decomposition. This represents substantial advance in catalytic H/D isotope exchange (HIE) reactions of C(sp3)−H bonds.

Highly Selective and Efficient Perdeuteration of n-Pentane via H/D Exchange Catalyzed by a Silica-Supported Hafnium-Iridium Bimetallic Complex.

A Surface OrganoMetallic Chemistry (SOMC) approach is used to prepare a novel hafnium-iridium catalyst immobilized on silica, HfIr/SiO2, featuring well-defined [≡SiOHf(CH2 tBu)2(μ-H)3IrCp*] surface sites. Unlike the monometallic analogous materials Hf/SiO2 and Ir/SiO2, which promote n-pentane deuterogenolysis through C-C bond scission, we demonstrate that under the same experimental conditions (1 bar D2, 250 °C, 3 h, 0.5 mol %), the heterobimetallic catalyst HfIr/SiO2 is highly efficient and selective for the perdeuteration of alkanes with D2, exemplified on n-pentane, without substantial deuterogenolysis (<2 % at 95 % conversion). Furthermore this HfIr/SiO2 catalyst is robust and can be re-used several times without evidence of decomposition. This represents substantial advance in catalytic H/D isotope exchange (HIE) reactions of C(sp3)-H bonds.

Oxygen Activation in Aromatic Ring Cleaving Salicylate Dioxygenase: Detection of Reaction Intermediates with a Nitro-substituted Substrate Analog.

Cupin dioxygenases such as salicylate 1,2-dioxygense (SDO) perform aromatic C-C bond scission via a 3-His motif tethered iron cofactor. Here, transient kinetics measurements are used to monitor the catalytic cycle of SDO by using a nitro-substituted substrate analog, 3-nitrogentisate. Compared to the natural substrate, the nitro group reduces the enzymatic kcat by 500-fold, thereby facilitating the detection and kinetic characterization of reaction intermediates. Sums and products of reciprocal relaxation times derived from kinetic measurements were found to be linearly dependent on O2 concentration, suggesting reversible formation of two distinct intermediates. Dioxygen binding to the metal cofactor takes place with a forward rate of 5.9×103 M-1 s-1: two orders of magnitude slower than other comparable ring-cleaving dioxygenses. Optical chromophore of the first intermediate is distinct from the in situ generated SDO Fe(III)-O2⋅- complex but closer to the enzyme-substrate precursor.

Full carbon upcycling of organophosphorus wastewater enabled by interface photolysis

The key of wastewater treatment is to reduce the toxicity of organic pollutants and ideally undergo mineralization, typically accompanying the formation of greenhouse gas CO2 in large amounts. Here, a full carbon upcycling strategy for efficient valorization of organic phosphorus (OPs) contaminants enabled by interface photolysis was developed, in which the van der Waals interface effect based on the interfacial heterojunction interaction could efficiently regulate the electron density of the UCN/CdS NPs photocatalyst interface to benefit the construction of the interface-orienteering electron pump and edge active sites. The synergistic catalysis of ·OH on the C sites and holes on the Cd sites at the photocatalyst interface edge could realize the complete photodegradation of glyphosate wastewater in 2 h to exclusively afford gas fuel CO (4124 μmol g−1) and glycine (86 %), which was likewise applicable to an extensive scope of OPs for nigh quantitative carbon upcycling. Quantum calculations elaborated that the Cd edge sites with the ability to enrich holes induced by the van der Waals interface effect could reduce the activation energy of CP bond cleavage of glyphosate activated by ·OH, resulting in CP bond scission selectivity of ca. 91.5 %, which is vital to full carbon upcycling. The oriented interface engineering offers a more eco-friendly photocatalytic protocol to facilitate both wastewater treatment and carbon resource recovery.