Direct Observation of Dynamic Bond Evolution in Single‐Atom Pt/C3N4 Catalysts

Single‐atom catalysts are promising platforms for heterogeneous catalysis, especially for clean energy conversion, storage, and utilization. Although great efforts have been made to examine the bonding and oxidation state of single‐atom catalysts before and/or after catalytic reactions, when information about dynamic evolution is not sufficient, the underlying mechanisms are often overlooked. Herein, we report the direct observation of the charge transfer and bond evolution of a single‐atom Pt/C₃N₄ catalyst in photocatalytic water splitting by synchronous illumination X‐ray photoelectron spectroscopy. Specifically, under light excitation, we observed Pt?N bond cleavage to form a Pt⁰ species and the corresponding C=N bond reconstruction; these features could not be detected on the metallic platinum‐decorated C₃N₄ catalyst. As expected, H₂ production activity (14.7 mmol h^?1 g^?1) was enhanced significantly with the single‐atom Pt/C₃N₄ catalyst as compared to metallic Pt‐C₃N₄ (0.74 mmol h^?1 g^?1).     

Molten‐Salt‐Mediated Synthesis of an Atomic Nickel Co‐catalyst on TiO2 for Improved Photocatalytic H2 Evolution

Atomic co‐catalysts offer high potential to improve the photocatalytic performance, of which the preparation with earth‐abundant elements is challenging. Here, a new molten salt method (MSM) is designed to prepare atomic Ni co‐catalyst on widely studied TiO₂ nanoparticles. The liquid environment and space confinement effect of the molten salt leads to atomic dispersion of Ni ions on TiO₂, while the strong polarizing force provided by the molten salt promotes formation of strong Ni?O bonds. Interestingly, Ni atoms are found to facilitate the formation of oxygen vacancies (OV) on TiO₂ during the MSM process, which benefits the charge transfer and hydrogen evolution reaction. The synergy of atomic Ni co‐catalyst and OV results in 4‐time increase in H₂ evolution rate compared to that of the Ni co‐catalyst on TiO₂ prepared by an impregnation method. This work provides a new strategy of controlling atomic co‐catalyst together with defects for efficient photocatalytic water splitting.     

A Noble‐Metal‐Free Nickel(II) Polypyridyl Catalyst for Visible‐Light‐Driven Hydrogen Production from Water

The complex [Ni(bpy)₃]²⁺ (bpy=2,2′‐bipyridine) is an active catalyst for visible‐light‐driven H₂ production from water when employed with [Ir(dfppy)₂(Hdcbpy)] [dfppy=2‐(3,4‐difluorophenyl)pyridine, Hdcbpy=4‐carboxy‐2,2′‐bipyridine‐4′‐carboxylate] as the photosensitizer and triethanolamine as the sacrificial electron donor. The highest turnover number of 520 with respect to the nickel(II) catalyst is obtained in a 8:2 acetonitrile/water solution at pH 9. The H₂‐evolution system is more stable after the addition of an extra free bpy ligand, owing to faster catalyst regeneration. The photocatalytic results demonstrate that the nickel(II) polypyridyl catalyst can act as a more effective catalyst than the commonly utilized [Co(bpy)₃]²⁺. This study may offer a new paradigm for constructing simple and noble‐metal‐free catalysts for photocatalytic hydrogen production.     

Surface Functionalization of g‐C3N4: Molecular‐Level Design of Noble‐Metal‐Free Hydrogen Evolution Photocatalysts

A stable noble‐metal‐free hydrogen evolution photocatalyst based on graphite carbon nitride (g‐C₃N₄) was developed by a molecular‐level design strategy. Surface functionalization was successfully conducted to introduce a single nickel active site onto the surface of the semiconducting g‐C₃N₄. This catalyst family (with less than 0.1 wt % of Ni) has been found to produce hydrogen with a rate near to the value obtained by using 3 wt % platinum as co‐catalyst. This new catalyst also exhibits very good stability under hydrogen evolution conditions, without any evidence of deactivation after 24 h.     

Photocatalyzed Hydrogen Evolution from Water by a Composite Catalyst of NH2‐MIL‐125(Ti) and Surface Nickel(II) Species

A composite of the metal–organic framework (MOF) NH₂‐MIL‐125(Ti) and molecular and ionic nickel(II) species, catalyzed hydrogen evolution from water under UV light. In 95 v/v % aqueous conditions the composite produced hydrogen in quantities two orders of magnitude higher than that of the virgin framework and an order of magnitude greater than that of the molecular catalyst. In a 2 v/v % water and acetonitrile mixture, the composite demonstrated a TOF of 28 mol H₂ g(Ni)^?1 h^?1 and remained active for up to 50 h, sustaining catalysis for three times longer and yielding 20‐fold the amount of hydrogen. Appraisal of physical mixtures of the MOF and each of the nickel species under identical photocatalytic conditions suggest that similar surface localized light sensitization and proton reduction processes operate in the composite catalyst. Both nickel species contribute to catalytic conversion, although different activation behaviors are observed.     

A Methylthio‐Functionalized‐MOF Photocatalyst with High Performance for Visible‐Light‐Driven H2 Evolution

Recently, the emergence of photoactive metal–organic frameworks (MOFs) has given great prospects for their applications as photocatalytic materials in visible‐light‐driven hydrogen evolution. Herein, a highly photoactive visible‐light‐driven material for H₂ evolution was prepared by introducing methylthio terephthalate into a MOF lattice via solvent‐assisted ligand‐exchange method. Accordingly, a first methylthio‐functionalized porous MOF decorated with Pt co‐catalyst for efficient photocatalytic H₂ evolution was achieved, which exhibited a high quantum yield (8.90 %) at 420 nm by use sacrificial triethanolamine. This hybrid material exhibited perfect H₂ production rate as high as 3814.0 μmol g^?1 h^?1, which even is one order of magnitude higher than that of the state‐of‐the‐art Pt/MOF photocatalyst derived from aminoterephthalate.     

Graphitic Carbon Nitride Nanoribbons: Graphene‐Assisted Formation and Synergic Function for Highly Efficient Hydrogen Evolution

The development of new promising metal‐free catalysts is of great significance for the electrocatalytic hydrogen evolution reaction (HER). Herein, a rationally assembled three‐dimensional (3D) architecture of 1D graphitic carbon nitride (g‐C₃N₄) nanoribbons with 2D graphene sheets has been developed by a one‐step hydrothermal method. Because of the multipathway of charge and mass transport, the hierarchically structured g‐C₃N₄ nanoribbon–graphene hybrids lead to a high electrocatalytic ability for HER with a Tafel slope of 54 mV decade^?1, a low onset overpotential of 80 mV and overpotential of 207 mV to approach a current of 10 mA cm^?2, superior to those non‐metal materials and well‐developed metallic catalysts reported previously. This work presents a great advance for designing and developing highly efficient metal‐free catalyst for hydrogen evolution.     

Strong‐Base‐Assisted Synthesis of a Crystalline Covalent Triazine Framework with High Hydrophilicity via Benzylamine Monomer for Photocatalytic Water Splitting

Methods to synthesize crystalline covalent triazine frameworks (CTFs) are limited and little attention has been paid to development of hydrophilic CTFs and photocatalytic overall water splitting. A route to synthesize crystalline and hydrophilic CTF‐HUST‐A1 with a benzylamine‐functionalized monomer is presented. The base reagent used plays an important role in the enhancement of crystallinity and hydrophilicity. CTF‐HUST‐A1 exhibits good crystallinity, excellent hydrophilicity, and excellent photocatalytic activity in sacrificial photocatalytic hydrogen evolution (hydrogen evolution rate up to 9200 μmol g^?1 h^?1). Photocatalytic overall water splitting is achieved by depositing dual co‐catalysts in CTF‐HUST‐A1, with H₂ evolution and O₂ evolution rates of 25.4 μmol g^?1 h^?1 and 12.9 μmol g^?1 h^?1 in pure water without using sacrificial agent.     

Cost‐Efficient Graphitic Carbon Nitride as an Effective Photocatalyst for Antibiotic Degradation: An Insight into the Effects of Different Precursors and Coexisting Ions,and Photocatalytic Mechanism

In this study, the photocatalytic activity of graphitic carbon nitride (g‐C₃N₄) synthesized via different precursors (urea, thiourea, and dicyandiamide) is investigated in the degradation process of tetracycline. Owing to the efficient charge separation and transfer, prolonged radiative lifetime of charge, large surface area, and nanosheet morphology, the urea‐derived g‐C₃N₄ exhibits superior photocatalytic activity for tetracycline degradation under visible‐light irradiation. This performance can compare with that of most reported g‐C₃N₄‐based composite photocatalysts. Through the time‐circle degradation experiment, the urea‐derived g‐C₃N₄ is found to have an excellent photocatalytic stability. The presence of NO₃^?, CH₃COO^?, Cl^? and SO₄^2? ions with the concentration of 10 mm inhibits the photocatalytic activity of urea‐derived g‐C₃N₄, where this inhibitory effect is more obvious for Cl^? and SO₄^2? ions. For the coexisting Cu²⁺, Ca²⁺, and Zn²⁺ ions, the Cu²⁺ ion exhibits a significantly higher inhibitory effect than Ca²⁺ and Zn²⁺ ions for tetracycline degradation. However, both the inhibitory and facilitating effects are observed in the presence of Fe³⁺ ion with different concentration. The h⁺, ^.OH and ^.O₂^? radicals are confirmed as major oxidation species and a possible photocatalytic mechanism is proposed in a urea‐derived g‐C₃N₄ reaction system. This study is of important significance to promote the large‐scale application of g‐C₃N₄ photocatalysts in antibiotic wastewater purification.     

High‐Efficiency Oxygen Reduction to Hydrogen Peroxide Catalyzed by Nickel Single‐Atom Catalysts with Tetradentate N2O2 Coordination in a Three‐Phase Flow Cell

Carbon‐supported Ni^II single‐atom catalysts with a tetradentate Ni‐N₂O₂ coordination formed by a Schiff base ligand‐mediated pyrolysis strategy are presented. A Ni^II complex of the Schiff base ligand (R,R)‐(?)‐N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine was adsorbed onto a carbon black support, followed by pyrolysis of the modified carbon material at 300 °C in Ar. The Ni‐N₂O₂/C catalyst showed excellent performance for the electrocatalytic reduction of O₂ to H₂O₂ through a two‐electron transfer process in alkaline conditions, with a H₂O₂ selectivity of 96 %. At a current density of 70 mA cm^?2, a H₂O₂ production rate of 5.9 mol g_cat.^?1 h^?1 was achieved using a three‐phase flow cell, with good catalyst stability maintained over 8 h of testing. The Ni‐N₂O₂/C catalyst could electrocatalytically reduce O₂ in air to H₂O₂ at a high current density, still affording a high H₂O₂ selectivity (>90 %). A precise Ni‐N₂O₂ coordination was key to the performance.     

Graphitic C3N4 Decorated with CoP Co‐catalyst: Enhanced and Stable Photocatalytic H2 Evolution Activity from Water under Visible‐light Irradiation

In this work, graphitic C₃N₄ decorated with a CoP co‐catalyst (g‐C₃N₄/CoP) is reported for photocatalytic H₂ evolution reaction based on two‐step hydrothermal and phosphidation method. The structure of g‐C₃N₄/CoP is well confirmed by XRD, FTIR, TEM, XPS, and UV/Vis diffuse reflection spectra techniques. When the weight percentage of CoP loading is 3.4 wt % (g‐C₃N₄/CoP‐3.4 %), the highest H₂ evolution amount of 8.4×10² μmol g⁻¹ is obtained, which is 1.1×10³ times than that over pure g‐C₃N₄. This value also is comparable with that of g‐C₃N₄ loaded by the same amount of Pt. In cycling experiments, g‐C₃N₄/CoP‐3.4 % shows a stable photocatalytic activity. In addition, g‐C₃N₄/CoP‐3.4 % is an efficient photocatalyst for H₂ evolution under irradiation with natural solar light. Based on comparative photoluminescence emission spectra, photoelectrochemical I –t curves, EIS Nyquist plots, and polarization curves between g‐C₃N₄/CoP‐3.4 % and pure g‐C₃N₄, it is concluded that the presence of the CoP co‐catalyst accelerates the separation and transfer of photogenerated electrons of g‐C₃N₄, thus resulting in improved photocatalytic activity in the H₂ evolution reaction.     

MoB/g‐C3N4 Interface Materials as a Schottky Catalyst to Boost Hydrogen Evolution

Proton adsorption on metallic catalysts is a prerequisite for efficient hydrogen evolution reaction (HER). However, tuning proton adsorption without perturbing metallicity remains a challenge. A Schottky catalyst based on metal–semiconductor junction principles is presented. With metallic MoB, the introduction of n‐type semiconductive g‐C₃N₄ induces a vigorous charge transfer across the MoB/g‐C₃N₄ Schottky junction, and increases the local electron density in MoB surface, confirmed by multiple spectroscopic techniques. This Schottky catalyst exhibits a superior HER activity with a low Tafel slope of 46 mV dec^?1 and a high exchange current density of 17 μA cm^?2, which is far better than that of pristine MoB. First‐principle calculations reveal that the Schottky contact dramatically lowers the kinetic barriers of both proton adsorption and reduction coordinates, therefore benefiting surface hydrogen generation.     

The Role of a Dipeptide Outer‐Coordination Sphere on H2‐Production Catalysts: Influence on Catalytic Rates and Electron Transfer

The outer‐coordination sphere of enzymes acts to fine‐tune the active site reactivity and control catalytic rates, suggesting that incorporation of analogous structural elements into molecular catalysts may be necessary to achieve rates comparable to those observed in enzyme systems at low overpotentials. In this work, we evaluate the effect of an amino acid and dipeptide outer‐coordination sphere on [Ni(P^Ph₂N^Ph‐R₂)₂]²⁺ hydrogen production catalysts. A series of 12 new complexes containing non‐natural amino acids or dipeptides was prepared to test the effects of positioning, size, polarity and aromaticity on catalytic activity. The non‐natural amino acid was either 3‐(meta‐ or para‐aminophenyl)propionic acid terminated as an acid, an ester or an amide. Dipeptides consisted of one of the non‐natural amino acids coupled to one of four amino acid esters: alanine, serine, phenylalanine or tyrosine. All of the catalysts are active for hydrogen production, with rates averaging ～1000 s^?1, 40 % faster than the unmodified catalyst. Structure and polarity of the aliphatic or aromatic side chains of the C‐terminal peptide do not strongly influence rates. However, the presence of an amide bond increases rates, suggesting a role for the amide in assisting catalysis. Overpotentials were lower with substituents at the N‐phenyl meta position. This is consistent with slower electron transfer in the less compact, para‐substituted complexes, as shown in digital simulations of catalyst cyclic voltammograms and computational modeling of the complexes. Combining the current results with insights from previous results, we propose a mechanism for the role of the amino acid and dipeptide based outer‐coordination sphere in molecular hydrogen production catalysts.     

Construction of a 2D Graphene‐Like MoS2/C3N4 Heterojunction with Enhanced Visible‐Light Photocatalytic Activity and Photoelectrochemical Activity

A novel graphene‐like MoS₂/C₃N₄ (GL‐MoS₂/C₃N₄) composite photocatalyst has been synthesized by a facile ethylene glycol (EG)‐assisted solvothermal method. The structure and morphology of this GL‐MoS₂/C₃N₄ photocatalyst have been investigated by a wide range of characterization methods. The results showed that GL‐MoS₂ was uniformly distributed on the surface of GL‐C₃N₄ forming a heterostructure. The obtained composite exhibited strong absorbing ability in the ultraviolet (UV) and visible regions. When irradiated with visible light, the composite photocatalyst showed high activity superior to those of the respective individual components GL‐MoS₂ and GL‐C₃N₄ in the degradation of methyl orange. The enhanced photocatalytic activity of the composite may be attributed to the efficient separation of electron–hole pairs as a result of the matching band potentials between GL‐MoS₂ and GL‐C₃N₄. Furthermore, a photocatalytic mechanism for the composite material has been proposed, and the photocatalytic reaction kinetics has been measured. Moreover, GL‐MoS₂/C₃N₄ could serve as a novel sensor for trace amounts of Cu²⁺ since it exhibited good selectivity for Cu²⁺ detection in water.     

Coupling of Bifunctional CoMn‐Layered Double Hydroxide@Graphitic C3N4 Nanohybrids towards Efficient Photoelectrochemical Overall Water Splitting

The development of durable, low‐cost, and efficient photo‐/electrolysis for the oxygen and hydrogen evolution reactions (OER and HER) is important to fulfill increasing energy requirements. Herein, highly efficient and active photo‐/electrochemical catalysts, that is, CoMn‐LDH@g‐C₃N₄ hybrids, have been synthesized successfully through a facile in situ co‐precipitation method at room temperature. The CoMn‐LDH@g‐C₃N₄ composite exhibits an obvious OER electrocatalytic performance with a current density of 40 mA cm^?2 at an overpotential of 350 mV for water oxidation, which is 2.5 times higher than pure CoMn‐LDH nanosheets. For HER, CoMn‐LDH@g‐C₃N₄ (η₅₀=?448 mV) requires a potential close to Pt/C (η₅₀=?416 mV) to reach a current density of 50 mA cm². Furthermore, under visible‐light irradiation, the photocurrent density of the CoMn‐LDH@g‐C₃N₄ composite is 0.227 mA cm^?2, which is 2.1 and 3.8 time higher than pristine CoMn‐LDH (0.108 mA cm^?2) and g‐C₃N₄ (0.061 mA cm^?2), respectively. The CoMn‐LDH@g‐C₃N₄ composite delivers a current density of 10 mA cm^?2 at 1.56 V and 100 mA cm^?2 at 1.82 V for the overall water‐splitting reaction. Therefore, this work establishes the first example of pure CoMn‐LDH and CoMn‐LDH@g‐C₃N₄ hybrids as electrochemical and photoelectrochemical water‐splitting systems for both OER and HER, which may open a pathway to develop and explore other LDH and g‐C₃N₄ nanosheets as efficient catalysts for renewable energy applications.     

Atomic‐Level Insight into Optimizing the Hydrogen Evolution Pathway over a Co1‐N4 Single‐Site Photocatalyst

Knowledge of the photocatalytic H₂ evolution mechanism is of great importance for designing active catalysts toward a sustainable energy supply. An atomic‐level insight, design, and fabrication of single‐site Co₁‐N₄ composite as a prototypical photocatalyst for efficient H₂ production is reported. Correlated atomic characterizations verify that atomically dispersed Co atoms are successfully grafted by covalently forming a Co₁‐N₄ structure on g‐C₃N₄ nanosheets by atomic layer deposition. Different from the conventional homolytic or heterolytic pathway, theoretical investigations reveal that the coordinated donor nitrogen increases the electron density and lowers the formation barrier of key Co hydride intermediate, thereby accelerating H–H coupling to facilitate H₂ generation. As a result, the composite photocatalyst exhibits a robust H₂ production activity up to 10.8 μmol h⁻¹, 11 times higher than that of pristine counterpart.     

Moderately branched ultra‐high molecular weight polyethylene by using N,N′‐nickel catalysts adorned with sterically hindered dibenzocycloheptyl groups

Five examples of unsymmetrical 1,2‐bis (arylimino) acenaphthene ( L1 – L5 ), each containing one N‐2,4‐bis (dibenzocycloheptyl)‐6‐methylphenyl group and one sterically and electronically variable N‐aryl group, have been used to prepare the N,N′‐nickel (II) halide complexes, [1‐[2,4‐{(C₁₅H₁₃}₂–6‐MeC₆H₂N]‐2‐(ArN)C₂C₁₀H₆]NiX₂ (X = Br: Ar = 2,6‐Me₂C₆H₃ Ni1 , 2,6‐Et₂C₆H₃ Ni2 , 2,6‐i‐Pr₂C₆H₃ Ni3 , 2,4,6‐Me₃C₆H₂ Ni4 , 2,6‐Et₂–4‐MeC₆H₂ Ni5 ) and (X = Cl: Ar = 2,6‐Me₂C₆H₃ Ni6 , 2,6‐Et₂C₆H₃ Ni7 , 2,6‐i‐Pr₂C₆H₃ Ni8 , 2,4,6‐Me₃C₆H₂ Ni9 , 2,6‐Et₂–4‐MeC₆H₂ Ni10 ), in high yield. The molecular structures Ni3 and Ni7 highlight the extensive steric protection imparted by the ortho‐dibenzocycloheptyl group and the distorted tetrahedral geometry conferred to the nickel center. On activation with either Et₂AlCl or MAO, Ni1 – Ni10 exhibited very high activities for ethylene polymerization with the least bulky Ni1 the most active (up to 1.06  ×  10⁷ g PE mol^?1(Ni) h^?1 with MAO). Notably, these sterically bulky catalysts have a propensity towards generating very high molecular weight polyethylene with moderate levels of branching and narrow dispersities with the most hindered Ni3 and Ni8 affording ultra‐high molecular weight material (up to 1.5  ×  10⁶ g mol^?1). Indeed, both the activity and molecular weights of the resulting polyethylene are among the highest to be reported for this class of unsymmetrical 1,2‐bis (imino)acenaphthene‐nickel catalyst.     

Alkylaluminum activator effects on polyethylene branching using a N,N′‐nickel precatalyst appended with bulky 4,4′‐dimethoxybenzhydryl groups

Ten unsymmetrical N,N'‐bis (imino) acenaphthene‐nickel (II) halide complexes, [1‐[2,6‐{(4‐MeOC₆H₄)₂CH}₂–4‐MeC₆H₂N]‐2‐(ArN)C₂C₁₀H₆]NiX₂, each appended with one N‐2,6‐bis(4,4'‐dimethoxybenzhydryl)‐4‐methylphenyl group, have been synthesized and characterized. The molecular structures of Ni1 , Ni3 , Ni5 and Ni6 highlight the variation in steric protection afforded by the inequivalent N‐aryl groups; a distorted tetrahedral geometry is conferred about each nickel center. On activation with diethylaluminum chloride (Et₂AlCl) or methylaluminoxane (MAO), all complexes showed high activity at 30°C for the polymerization of ethylene with the least bulky bromide precatalysts ( Ni1 and Ni4 ), generally the most productive, forming polyethylenes with narrow dispersities [M_w/M_n: < 3.4 (Et₂AlCl), < 4.1 (MAO)] and various levels of branching. Significantly, this level of branching can be influenced by the type of co‐catalyst employed, with Et₂AlCl having a predilection towards polymers displaying significantly higher branching contents than with MAO [T_m: 33.0–82.5°C (Et₂AlCl) vs. 117.9–119.4°C (MAO)]. On the other hand, the molecular weights of the materials obtained with each co‐catalyst were high and, in some cases, entering the ultra‐high molecular weight range [M_w range: 6.8–12.2 × 10⁵ g mol^?1 (Et₂AlCl), 7.2–10.9 × 10⁵ g mol^?1 (MAO)]. Furthermore, good tensile strength (ε_b up to 553.5%) and elastic recovery (up to 84%) have been displayed by selected more branched polymers highlighting their elastomeric properties.     

Enhanced catalytic performance of Pd‐Ga bimetallic catalysts for 2‐ethylanthraquinone hydrogenation

A series of Pd and Pd‐Ga bimetallic catalysts were prepared by a co‐impregnation method for 2‐ethylanthraquinone (EAQ) hydrogenation to produce hydrogen peroxide. Compared with 0.6Pd catalyst, the hydrogenation efficiency of 0.6Pd1.2Ga catalyst (11.9 g L^?1) increases by 32.2%, and the stability of 0.6Pd1.2Ga catalyst is also higher than that of 0.6Pd catalyst. The structures of the samples were determined by N₂ adsorption–desorption, ICP, XRD, CO chemisorption, TEM, H₂‐TPR, in situ CO‐DRIFTS and XPS. The results suggest that incorporation of Ga species improves Pd dispersion and generates a strong interaction between Ga₂O₃ and Pd interface or between Pd and support. DFT calculation results indicate that the strong adsorption of carbonyl group on Ga₂O₃/Pd interface facilitates the activation of EAQ and promotes the hydrogenation efficiency.     

Phase‐Contact Engineering in Mono‐ and Bimetallic Cu‐Ni Co‐catalysts for Hydrogen Photocatalytic Materials

Understanding how a photocatalyst modulates its oxidation state, size, and structure during a photocatalytic reaction under operando conditions is strongly limited by the mismatch between (catalyst) volume sampled by light and, to date, the physicochemical techniques and probes employed to study them. A synchrotron micro‐beam X‐ray absorption spectroscopy study together with the computational simulation and analysis (at the X‐ray cell) of the light‐matter interaction occurring in powdered TiO₂‐based monometallic Cu, Ni and bimetallic CuNi catalysts for hydrogen production from renewables was carried out. The combined information unveils an unexpected key catalytic role involving the phase contact between the reduced and oxidized non‐noble metal phases in all catalysts and, additionally, reveals the source of the synergistic Cu‐Ni interaction in the bimetallic material. The experimental method is applicable to operando studies of a wide variety of photocatalytic materials.