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).     

Non-Interacting Ni and Fe Dual-Atom Pair Sites in N-Doped Carbon Catalysts for Efficient Concentrating Solar-Driven Photothermal CO2 Reduction

Solar-to-chemical energy conversion under weak solar irradiation is generally difficult to meet the heat demand of CO₂ reduction. Herein, a new concentrated solar-driven photothermal system coupling a dual-metal single-atom catalyst (DSAC) with adjacent Ni−N₄ and Fe−N₄ pair sites is designed for boosting gas-solid CO₂ reduction with H₂O under simulated solar irradiation, even under ambient sunlight. As expected, the (Ni, Fe)−N−C DSAC exhibits a superior photothermal catalytic performance for CO₂ reduction to CO (86.16 μmol g⁻¹ h⁻¹), CH₄ (135.35 μmol g⁻¹ h⁻¹) and CH₃OH (59.81 μmol g⁻¹ h⁻¹), which are equivalent to 1.70-fold, 1.27-fold and 1.23-fold higher than those of the Fe−N−C catalyst, respectively. Based on theoretical simulations, the Fermi level and d-band center of Fe atom is efficiently regulated in non-interacting Ni and Fe dual-atom pair sites with electronic interaction through electron orbital hybridization on (Ni, Fe)−N−C DSAC. Crucially, the distance between adjacent Ni and Fe atoms of the Ni−N−N−Fe configuration means that the additional Ni atom as a new active site contributes to the main *COOH and *HCO₃ dissociation to optimize the corresponding energy barriers in the reaction process, leading to specific dual reaction pathways (COOH and HCO₃ pathways) for solar-driven photothermal CO₂ reduction to initial CO production.     

Organic Photovoltaic Catalyst with σ-π Anchor for High-Performance Solar Hydrogen Evolution

Efficient in situ deposition of metallic cocatalyst, like zero-valent platinum (Pt), on organic photovoltaic catalysts (OPCs) is the prerequisite for their high catalytic activities. Here we develop the OPC (Y6CO), by introducing carbonyl in the core, which is available to σ-π coordinate with transition metals, due to the high-energy empty π* orbital of carbonyl. Y6CO exhibits a stronger capability to anchor Pt species and reduce them to metallic state, resulting in more Pt⁰ deposition, relative to the control OPC without the central σ-π anchor. Single-component and heterojunction nanoparticles (NPs) employing Y6CO show enhanced average hydrogen evolution rates of 230.98 and 323.22 mmol h⁻¹ g_[OPC]⁻¹, respectively, under AM 1.5G, 100 mW cm⁻² for 10 h, and heterojunction NPs yield the external quantum efficiencies of ca. 10 % in 500–800 nm. This work demonstrates that σ-π anchoring is one efficient strategy for integrating metallic cocatalyst and OPC for high-performance photocatalysis.     

Pulsed Electrocatalysis Enabling High Overall Nitrogen Fixation Performance for Atomically Dispersed Fe on TiO2

Atomically dispersed Fe was designed on TiO₂ and explored as a Janus electrocatalyst for both nitrogen oxidation reaction (NOR) and nitrogen reduction reaction (NRR) in a two-electrode system. Pulsed electrochemical catalysis (PE) was firstly involved to inhibit the competitive hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Excitingly, an unanticipated yield of 7055.81 μmol h⁻¹ g⁻¹_cat. and 12 868.33 μmol h⁻¹ g⁻¹_cat. were obtained for NOR and NRR at 3.5 V, respectively, 44.94 times and 7.8 times increase in FE than the conventional constant voltage electrocatalytic method. Experiments and density functional theory (DFT) calculations revealed that the single-atom Fe could stabilize the oxygen vacancy, lower the energy barrier for the vital rupture of N≡N, and result in enhanced N₂ fixation performance. More importantly, PE could effectively enhance the N₂ supply by reducing competitive O₂ and H₂ agglomeration, inhibit the electrocatalytic by-product formation for longstanding *OOH and *H intermediates, and promote the non-electrocatalytic process of N₂ activation.     

Engineering a Self-Grown TiO2/Ti-MOF Heterojunction with Selectively Anchored High-Density Pt Single-Atomic Cocatalysts for Efficient Visible-Light-Driven Hydrogen Evolution

A photocatalyst TiO₂/Ti-BPDC-Pt is developed with a self-grown TiO₂/Ti-metal–organic framework (MOF) heterojunction, i.e., TiO₂/Ti-BPDC, and selectively anchored high-density Pt single-atomic cocatalysts on Ti-BPDC for photocatalytic hydrogen evolution. This intimate heterojunction, growing from the surface pyrolytic reconstruction of Ti-BPDC, works in a direct Z-scheme, efficiently separating electrons and holes. Pt is selectively anchored on Ti-BPDC by ligands and is found in the form of single atoms with loading up to 1.8 wt %. The selective location of Pt is the electron-enriched domain of the heterojunction, which further enhances the utilization of the separated electrons. This tailored TiO₂/Ti-BPDC-Pt shows a significantly enhanced activity of 12.4 mmol g⁻¹ h⁻¹ compared to other TiO₂- or MOF-based catalysts. The structure-activity relationship further proves the balance of two simultaneously exposed domains of heterojunctions is critical to fulfilling this kind of catalyst.     

CdS nanospheres hybridized with graphitic C3N4 for effective photocatalytic hydrogen generation under visible light irradiation

Graphitic carbon nitride (g‐C₃N₄)‐based photocatalysts have received considerable attention in the field of photocatalysis, especially for photocatalytic H₂ evolution. However, the intrinsic disadvantages of g‐C₃N₄ seriously limit its practical application. Herein, CdS nanospheres with an average diameter of 135 nm prepared using a solvothermal method were used as co‐catalysts to form CdS/g‐C₃N₄ composites (CSCN) to enhance the photocatalytic activity. Various techniques were employed to characterize the structure, composition and optical properties of the as‐prepared samples. It was found that the CdS nanospheres were relatively uniformly dispersed on the surface of g‐C₃N₄. Moreover, the photocatalytic H₂ generation activity of the samples was evaluated using lactic acid as sacrificial reagent in water under visible light irradiation. When the amount of CdS nanospheres loaded in the hybridized composites was 5 wt%, the optimal H₂ evolution rate reached 924 μmol g^?1 h^?1, which was approximately 1.4 times higher than that (680 μmol g^?1 h^?1) of Pt/g‐C₃N₄ (3 wt%). Based on the results of analysis, a possible mechanism for the photocatalytic activity of CSCN is proposed tentatively.     

Graphitic Carbon Nitride/Nitrogen‐Rich Carbon Nanofibers: Highly Efficient Photocatalytic Hydrogen Evolution without Cocatalysts

An interconnected framework of mesoporous graphitic‐C₃N₄ nanofibers merged with in situ incorporated nitrogen‐rich carbon has been prepared. The unique composition and structure of the nanofibers as well as strong coupling between the components endow them with efficient light‐harvesting properties, improved charged separation, and a multidimensional electron transport path that enhance the performance of hydrogen production. The as‐obtained catalyst exhibits an extremely high hydrogen‐evolution rate of 16885 μmol h^?1 g^?1, and a remarkable apparent quantum efficiency of 14.3 % at 420 nm without any cocatalysts, which is much higher than most reported g‐C₃N₄‐based photocatalysts even in the presence of Pt‐based cocatalysts.     

One-Step Preparation of Fe/N/C Single-Atom Catalysts Containing Fe−N4 Sites from an Iron Complex Precursor with 5,6,7,8-Tetraphenyl-1,12-Diazatriphenylene Ligands

Fe/N/C single-atom catalysts containing Fe−N_x sites prepared by pyrolysis are promising cathode materials for fuel cells and metal-air batteries due to their high oxygen reduction reaction (ORR) activities. We have developed iron complexes containing N2- or N3-chelating coordination structures with preorganized aromatic rings in a 1,12-diazatriphenylene framework tethering bromo substituents as precursors to precisely construct Fe−N₄ sites in an Fe/N/C catalyst. One-step pyrolysis of the iron complex with carbon black forms atomically dispersed Fe−N₄ sites without iron aggregates. X-ray absorption spectroscopy (XAS) and electrochemical measurements revealed that the iron complex with N3-coordination is more effectively converted to Fe−N₄ sites catalyzing ORR with a TOF value of 0.21 e site⁻¹ s⁻¹ at 0.8 V vs. RHE. This indicates that the formation of Fe−N₄ sites is controlled by precise tuning of the chemical structure of the iron complex precursor.     

Inside Cover: Mechanistic Understanding of Efficient Polyethylene Hydrocracking over Two-Dimensional Platinum-Anchored Tungsten Trioxide (Angew. Chem. Int. Ed. 40/2023)

Chemical upcycling of polyethylene (PE) can convert plastic waste into valuable resources. However, engineering a catalyst that allows PE decomposition at low temperatures with high activity remains a significant challenge. Herein, we anchored 0.2 wt.% platinum (Pt) on defective two-dimensional tungsten trioxide (2D WO₃) nanosheets and achieved hydrocracking of high-density polyethylene (HDPE) waste at 200–250 °C with a liquid fuel (C_5–18) formation rate up to 1456 g_products ⋅ g_{metal species}⁻¹ ⋅ h⁻¹. The reaction pathway over the bifunctional 2D Pt/WO₃ is elucidated by quasi-operando transmission infrared spectroscopy, where (I) well-dispersed Pt immobilized on 2D WO₃ nanosheets trigger the dissociation of hydrogen; (II) adsorption of PE and activation of C−C cleavage on WO₃ are through the formation of C=O/C=C intermediates; (III) intermediates are converted to alkane products by the dissociated H. Our study directly illustrates the synergistic role of bifunctional Pt/WO₃ catalyst in the hydrocracking of HDPE, paving the way for the development of high-performance catalysts with optimized chemical and morphological properties.     

Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

Propane dehydrogenation (PDH) has great potential to meet the increasing global demand for propylene, but the widely used Pt-based catalysts usually suffer from short-term stability and unsatisfactory propylene selectivity. Herein, we develop a ligand-protected direct hydrogen reduction method for encapsulating subnanometer bimetallic Pt–Zn clusters inside silicalite-1 (S-1) zeolite. The introduction of Zn species significantly improved the stability of the Pt clusters and gave a superhigh propylene selectivity of 99.3 % with a weight hourly space velocity (WHSV) of 3.6–54 h⁻¹ and specific activity of propylene formation of 65.5 mol g_Pt⁻¹ h⁻¹ (WHSV=108 h⁻¹) at 550 °C. Moreover, no obvious deactivation was observed over PtZn4@S-1-H catalyst even after 13000 min on stream (WHSV=3.6 h⁻¹), affording an extremely low deactivation constant of 0.001 h⁻¹, which is 200 times lower than that of the PtZn4/Al₂O₃ counterpart under the same conditions. We also show that the introduction of Cs⁺ ions into the zeolite can improve the regeneration stability of catalysts, and the catalytic activity kept unchanged after four continuous cycles.     

One-Step Approach for Constructing High-Density Single-Atom Catalysts toward Overall Water Splitting at Industrial Current Densities

The construction of highly active, durable, and cost-effective catalysts is urgently needed for green hydrogen production. Herein, catalysts consisting of high-density Pt (24 atoms nm⁻²) and Ir (32 atoms nm⁻²) single atoms anchored on Co(OH)₂ were constructed by a facile one-step approach. Remarkably, Pt₁/Co(OH)₂ and Ir₁/Co(OH)₂ only required 4 and 178 mV at 10 mA cm⁻² for hydrogen evolution reaction and oxygen evolution reaction, respectively. Moreover, the assembled Pt₁/Co(OH)₂//Ir₁/Co(OH)₂ system showed mass activity of 4.9 A mg_{noble metal}⁻¹ at 2.0 V in an alkaline water electrolyzer, which is 316.1 times higher than that of Pt/C//IrO₂. Mechanistic studies revealed that reconstructed Ir−O₆ single atoms and remodeled Pt triple-atom sites enhanced the occupancy of Ir−O bonding orbitals and improved the occupation of Pt−H antibonding orbital, respectively, contributing to the formation of the O−O bond and the desorption of hydrogen. This one-step approach was also generalized to fabricate other 20 single-atom catalysts.     

Disclosing Support-Size-Dependent Effect on Ambient Light-Driven Photothermal CO2 Hydrogenation over Nickel/Titanium Dioxide

The size of support in heterogeneous catalysts can strongly affect the catalytic property but is rarely explored in light-driven catalysis. Herein, we demonstrate the size of TiO₂ support governs the selectivity in photothermal CO₂ hydrogenation by tuning the metal-support interactions (MSI). Small-size TiO₂ loading nickel (Ni/TiO₂-25) with enhanced MSI promotes photo-induced electrons of TiO₂ migrating to Ni nanoparticles, thus favoring the H₂ cleavage and accelerating the CH₄ formation (227.7 mmol g⁻¹ h⁻¹) under xenon light-induced temperature of 360 °C. Conversely, Ni/TiO₂-100 with large TiO₂ prefers yielding CO (94.2 mmol g⁻¹ h⁻¹) due to weak MSI, inefficient charge separation, and inadequate supply of activated hydrogen. Under ambient solar irradiation, Ni/TiO₂-25 achieves the optimized CH₄ rate (63.0 mmol g⁻¹ h⁻¹) with selectivity of 99.8 %, while Ni/TiO₂-100 exhibits the CO selectivity of 90.0 % with rate of 30.0 mmol g⁻¹ h⁻¹. This work offers a novel approach to tailoring light-driven catalytic properties by support size effect.     

Highly Effective Ru/BaCeO3 Catalysts on Supports with Strong Basic Sites for Ammonia Synthesis

BaCeO₃‐a and BaCeO₃‐b, with strong basic sites, were synthesized by using a co‐precipitation method at different calcination temperatures, and used as supports to evaluate their performance in ammonia synthesis. The ammonia synthesis rate with the 1.25 % Ru/BaCeO₃‐a catalyst is 24 mmol g^?1 h^?1, which is higher than that of 1.25 % Ru/BaCeO₃‐b catalyst (18 mmol g^?1 h^?1) at 3 MPa and 450 °C. Moreover, the performance of the 4 % Cs‐1.25 % Ru/BaCeO₃‐a catalyst was further improved to 28 mmol g^?1 h^?1, and no sign of deactivation was observed after a reaction time of 120 h. The XPS and H₂ temperature‐programmed reduction analyses indicated that the Ru/BaCeO₃‐a catalyst has more oxygen vacancies than the Ru/BaCeO₃‐b catalyst. In addition, the average Ru particle size of the Ru/BaCeO₃‐a catalyst is closer to 2 nm than the Ru/BaCeO₃‐b catalyst, which promotes the generation of B₅‐type sites (the active site for N₂ dissociation). The CO₂ temperature‐programmed desorption analysis indicates that BaCeO₃‐a has a high basic density, which is beneficial for electron transfer to Ru and further facilitates the dissociation of N≡N bonds.     

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.     

Breaking Local Charge Symmetry of Iron Single Atoms for Efficient Electrocatalytic Nitrate Reduction to Ammonia

The electrochemical conversion of nitrate pollutants into value-added ammonia is a feasible way to achieve artificial nitrogen cycle. However, the development of electrocatalytic nitrate-to-ammonia reduction reaction (NO₃⁻RR) has been hampered by high overpotential and low Faradaic efficiency. Here we develop an iron single-atom catalyst coordinated with nitrogen and phosphorus on hollow carbon polyhedron (denoted as Fe−N/P−C) as a NO₃⁻RR electrocatalyst. Owing to the tuning effect of phosphorus atoms on breaking local charge symmetry of the single-Fe-atom catalyst, it facilitates the adsorption of nitrate ions and enrichment of some key reaction intermediates during the NO₃⁻RR process. The Fe−N/P−C catalyst exhibits 90.3 % ammonia Faradaic efficiency with a yield rate of 17980 μg h⁻¹ mg_cat⁻¹, greatly outperforming the reported Fe-based catalysts. Furthermore, operando SR-FTIR spectroscopy measurements reveal the reaction pathway based on key intermediates observed under different applied potentials and reaction durations. Density functional theory calculations demonstrate that the optimized free energy of NO₃⁻RR intermediates is ascribed to the asymmetric atomic interface configuration, which achieves the optimal electron density distribution. This work demonstrates the critical role of atomic-level precision modulation by heteroatom doping for the NO₃⁻RR, providing an effective strategy for improving the catalytic performance of single atom catalysts in different electrochemical reactions.     

Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

A Janus Fe-SnO2 Catalyst that Enables Bifunctional Electrochemical Nitrogen Fixation

Electrochemical N₂ reduction reactions (NRR) and the N₂ oxidation reaction (NOR), using H₂O and N₂, are a sustainable approach to N₂ fixation. To date, owing to the chemical inertness of nitrogen, emerging electrocatalysts for the electrochemical NRR and NOR at room temperature and atmospheric pressure remain largely underexplored. Herein, a new-type Fe-SnO₂ was designed as a Janus electrocatalyst for achieving highly efficient NRR and NOR catalysis. A high NH₃ yield of 82.7 μg h⁻¹ mg_cat.⁻¹ and a Faraday efficiency (FE) of 20.4 % were obtained for NRR. This catalyst can also serve as an excellent NOR electrocatalyst with a NO₃⁻ yields of 42.9 μg h⁻¹ mg_cat.⁻¹ and a FE of 0.84 %. By means of experiments and DFT calculations, it is revealed that the oxygen vacancy-anchored single-atom Fe can effectively adsorb and activate chemical inert N₂ molecules, lowering the energy barrier for the vital breakage of N≡N and resulting in the enhanced N₂ fixation performance.     

Electrocatalytically Active Fe-(O-C2)4 Single-Atom Sites for Efficient Reduction of Nitrogen to Ammonia

Single-atom catalysts have demonstrated their superiority over other types of catalysts for various reactions. However, the reported nitrogen reduction reaction single-atom electrocatalysts for the nitrogen reduction reaction exclusively utilize metal–nitrogen or metal–carbon coordination configurations as catalytic active sites. Here, we report a Fe single-atom electrocatalyst supported on low-cost, nitrogen-free lignocellulose-derived carbon. The extended X-ray absorption fine structure spectra confirm that Fe atoms are anchored to the support via the Fe-(O-C₂)₄ coordination configuration. Density functional theory calculations identify Fe-(O-C₂)₄ as the active site for the nitrogen reduction reaction. An electrode consisting of the electrocatalyst loaded on carbon cloth can afford a NH₃ yield rate and faradaic efficiency of 32.1 μg h⁻¹ mg_cat.⁻¹ (5350 μg h⁻¹ mg_Fe⁻¹) and 29.3 %, respectively. An exceptional NH₃ yield rate of 307.7 μg h⁻¹ mg_cat.⁻¹ (51 283 μg h⁻¹ mg_Fe⁻¹) with a near record faradaic efficiency of 51.0 % can be achieved with the electrocatalyst immobilized on a glassy carbon electrode.     

Modulating Metal-Nitrogen Coupling in Anti-Perovskite Nitride via Cation Doping for Efficient Reduction of Nitrate to Ammonia

The complexes of metal center and nitrogen ligands are the most representative systems for catalyzing hydrogenation reactions in small molecule conversion. Developing heterogeneous catalysts with similar active metal-nitrogen functional centers, nevertheless, still remains challenging. In this work, we demonstrate that the metal-nitrogen coupling in anti-perovskite Co₄N can be effective modulated by Cu doping to form Co₃CuN, leading to strongly promoted hydrogenation process during electrochemical reduction of nitrate (NO₃⁻RR) to ammonia. The combination of advanced spectroscopic techniques and density functional theory calculations reveal that Cu dopants strengthen the Co−N bond and upshifted the metal d-band towards the Fermi level, promoting the adsorption of NO₃⁻ and *H and facilitating the transition from *NO₂/*NO to *NO₂H/*NOH. Consequently, the Co₃CuN delivers noticeably better NO₃⁻RR activity than the pristine Co₄N, with optimal Faradaic efficiency of 97 % and ammonia yield of 455.3 mmol h⁻¹ cm⁻² at −0.3 V vs. RHE. This work provides an effective strategy for developing high-performance heterogeneous catalyst for electrochemical synthesis.     

Highly Dispersed and Small‐Sized Nickel(II) Hydroxide Co‐Catalyst Prepared by Photodeposition for Hydrogen Production

Photodeposition has been widely used as a mild and efficient synthetic method to deposit co‐catalysts. It is also worth studying how to synthesize non‐noble metal photocatalysts with uniform dispersion. Different synthetic conditions in photodeposition have a certain influence on particle size distribution and photocatalytic activity. Therefore, we designed experiments to prepare the inexpensive composite photocatalyst Ni(OH)₂/g‐C₃N₄ by photodeposition. The Ni(OH)₂ co‐catalysts disperse uniformly with particle sizes of about 10 nm. The photocatalytic hydrogen production rate of Ni(OH)₂/g‐C₃N₄ reached about 19 mmol g^?1 h^?1, with the Ni(OH)₂ deposition amount about 1.57 %. During 16 h stability testing, the rate of hydrogen production did not decrease significantly. The composite catalyst also revealed a good hydrogen production performance under sunlight. The Ni(OH)₂ co‐catalyst enhanced the separation ability of photogenerated carriers, which was proved by surface photovoltage and fluorescence analysis.