Boronization‐Induced Ultrathin 2D Nanosheets with Abundant Crystalline–Amorphous Phase Boundary Supported on Nickel Foam toward Efficient Water Splitting

The conversion of crystalline metal–organic frameworks (MOFs) into metal compounds/carbon hybrid nanocomposites via pyrolysis provides a promising solution to design electrocatalysts for electrochemical water splitting. However, pyrolyzing MOFs generally involves a complex high‐temperature treatment, which can destroy the coordinated surroundings within MOFs, and as a result not taking their full advantage of their electrolysis properties. Herein, a simple and room‐temperature boronization strategy is developed to convert nickel zeolite imidazolate framework (Ni‐ZIF) nanorods into ultrathin Ni‐ZIF/Ni? B nanosheets with abundant crystalline–amorphous phase boundaries. The combined experiment, and theoretical calculation results disclose that the ultrathin thickness allows fast electron transfer and ensures increased exposure of surface coordinatively unsaturated active sites while the crystalline–amorphous interface elaborately changes the potential‐determining step to energetically favorable intermediates. As a result, Ni‐ZIF/Ni? B nanosheets supported on nickel foam (NF) require overpotentials of 67 mV for the hydrogen evolution reaction and 234 mV for the oxygen evolution reaction to achieve a current density of 10 mA cm^?2. Remarkably, Ni‐ZIF/Ni? B@NF as a bifunctional electrocatalyst for overall water splitting enables an alkaline electrolyzer with 10 mA cm^?2 at an ultralow cell voltage of 1.54 V. The present work may open a new avenue to the design of MOF‐derived composites for electrocatalysis.     

Enhancing Mo:BiVO4 Solar Water Splitting with Patterned Au Nanospheres by Plasmon‐Induced Energy Transfer

Plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon‐induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum‐doped bismuth vanadium oxide (Mo:BiVO₄), regarded as one of the best metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO₄ photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO₄. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time‐correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO₄ at 1.23 V versus RHE by ≈2.2‐fold (2.83 mA cm^?2).     

Donor‐Acceptor Interfacial Interactions Dominate Device Performance in Hybrid P3HT‐ZnO Nanowire‐Array Solar Cells

The adsorption of self‐assembled monolayers (SAMs) on metal oxide surfaces is a promising route to control electronic characteristics and surface wettability. Here, arylphosphonic acid derivatives are used to modulate the surface properties of vertically oriented ZnO nanowire arrays. Arylphosphonate‐functionalized ZnO nanowires are incorporated into hybrid organic‐inorganic solar cells in which infiltrated poly(3‐hexylthiophene) (P3HT) serves as the polymer donor. Strong correlations between device short‐circuit current density (J _sc) and power conversion efficiencies (PCEs) with ZnO surface functionalization species are observed and a weak correlation in the open‐circuit voltage (V _oc) is observed. Inverted solar cells fabricated with these treated interfaces exhibit PCEs as high as 2.1%, primarily due to improvements in J _sc. Analogous devices using untreated ZnO arrays having efficiencies of 1.6%. The enhancement in J _sc is attributed to surface passivation of ZnO by SAMs and enhanced wettability from P3HT, which improve charge transfer and reduce carrier recombination at the organic‐inorganic interface in the solar cells.     

Moisture‐Assisted Preparation of Compact GaN:ZnO Photoanode Toward Efficient Photoelectrochemical Water Oxidation

Developing strategies that can promote charge transportation in photodevices is crucial for achieving high solar energy conversion efficiency. Herein a moisture‐assisted nitridation approach is presented for the fabrication of efficient gallium‐zinc oxynitride (GaN:ZnO) photoanode with compact structure to facilitate the charge transportation. With moisture‐assisted nitridation, the charge separation efficiency and injection efficiency obtained on GaN:ZnO photoanode are significantly enhanced. Correspondingly, the photocurrent at 1.23 V vs reversible hydrogen electrode (RHE) has 18 folds improvement compared with that prepared without moisture assistance. Furthermore, via treating with HCl acid and modification with cobalt phosphate (CoPi) as a cocatalyst, state‐of‐the‐art photocurrent over 2.0 mA cm^?2 is achieved on independent GaN:ZnO photoanode when bias is higher than 1.4 V vs RHE. To the best of our knowledge, this is the first paradigm of moisture‐assisted preparing oxynitride‐based photoanode. The participation of moisture is found to improve the interconnection between adjacent GaN:ZnO nanoparticles as well as that between the GaN:ZnO film and the underlying substrate. Moreover, the volatilization of Zn can be substantially suppressed due to the modulation of reaction pathway by moisture. These two factors are confirmed to be the main reasons for the enhanced charge transportation and PEC performance obtained on GaN:ZnO photoanode.     

In Situ Grown Bimetallic MOF‐Based Composite as Highly Efficient Bifunctional Electrocatalyst for Overall Water Splitting with Ultrastability at High Current Densities

A newly designed water‐stable NH₂‐MIL‐88B(Fe₂Ni)‐metal–organic framework (MOF), in situ grown on the surface of a highly conducting 3D macroporous nickel foam (NF), termed NFN‐MOF/NF, is demonstrated to be a highly efficient bifunctional electrocatalyst for overall water splitting with ultrastability at high current densities. The NFN‐MOF/NF achieves ultralow overpotentials of 240 and 87 mV at current density of 10 mA cm^?2 for the oxygen evolution reaction and hydrogen evolution reaction, respectively, in 1 m KOH. For the overall water splitting, it requires only an ultralow cell voltage of 1.56 V to reach the current density of 10 mA cm^?2, outperforming the pairing of Pt/C on NF as the cathode and IrO₂ on NF as the anode at the same catalyst loading. The stability of the NFN‐MOF/NF catalyst is also outstanding, exhibiting only a minor chronopotentiometric decay of 7.8% at 500 mA cm^?2 after 30 h. The success of the present NFN‐MOF/NF catalyst is attributed to the abundant active centers, the bimetallic clusters {Fe₂Ni(µ₃‐O)(COO)₆(H₂O)₃}, in the MOF, the positive coupling effect between Ni and Fe metal ions in the MOF, and synergistic effect between the MOF and NF.     

Oriented Transformation of Co‐LDH into 2D/3D ZIF‐67 to Achieve Co–N–C Hybrids for Efficient Overall Water Splitting

Construction of well‐defined metal–organic framework precursor is vital to derive highly efficient transition metal–carbon‐based electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Herein, a novel strategy involving an in situ transformation of ultrathin cobalt layered double hydroxide into 2D cobalt zeolitic imidazolate framework (ZIF‐67) nanosheets grafted with 3D ZIF‐67 polyhedra supported on the surface of carbon cloth (2D/3D ZIF‐67@CC) precursor is proposed. After a low‐temperature pyrolysis, this precursor can be further converted into hybrid composites composed of ultrafine cobalt nanoparticles embedded within 2D N‐doped carbon nanosheets and 3D N‐doped hollow carbon polyhedra (Co@N‐CS/N‐HCP@CC). Experimental and density functional theory calculations results indicate that such composites have the advantages of a large number of accessible active sites, accelerated charge/mass transfer ability, the synergistic effect of components as well as an optimal water adsorption energy change. As a result, the obtained Co@N‐CS/N‐HCP@CC catalyst requires overpotentials of only 66 and 248 mV to reach a current density of 10 mA cm^?2 for HER and OER in 1.0 m KOH, respectively. Remarkably, it enables an alkali‐electrolyzer with a current density of 10 mA cm^?2 at a low cell voltage of 1.545 V, superior to that of the IrO₂@CC||Pt/C@CC couple (1.592 V).     

One‐Step Fabrication of Ultrathin Porous Nickel Hydroxide‐Manganese Dioxide Hybrid Nanosheets for Supercapacitor Electrodes with Excellent Capacitive Performance

A facile one‐step hydrothermal co‐deposition method for growth of ultrathin Ni(OH)₂‐MnO₂ hybrid nanosheet arrays on three dimensional (3D) macroporous nickel foam is presented. Due to the highly hydrophilic and ultrathin nature of hybrid nanosheets, as well as the synergetic effects of Ni(OH)₂ and MnO₂, the as‐fabricated Ni(OH)₂‐MnO₂ hybrid electrode exhibits an ultrahigh specific capacitance of 2628 F g^?1. Moreover, the asymmetric supercapacitor with the as‐obtained Ni(OH)₂‐MnO₂ hybrid film as the positive electrode and the reduced graphene oxide as the negative electrode has a high energy density (186 Wh kg^?1 at 778 W kg^?1), based on the total mass of active materials.     

3D Porous Pyramid Heterostructure Array Realizing Efficient Photo‐Electrochemical Performance

Direct photo‐electrochemical (PEC) water splitting is of great practical interest for developing a sustainable energy systems, but remains a big challenge owing to sluggish charge separation, low efficiency, and poor stability. Herein, a 3D porous In₂O₃/In₂S₃ pyramid heterostructure array on a fluorine‐doped tin oxide substrate is fabricated by an ion exchange–induced synthesis strategy. Based on the synergistic structural and electronic modulations from density functional theory calculations and experimental observations, 3D porous In₂O₃/In₂S₃ photoanode by the protective layer delivers a low onset potential of ≈0.02 V versus reversible hydrogen electrode (RHE), the highest photocurrent density of 8.2 mA cm^?2 at 1.23 V versus RHE among all the In₂S₃ photoanodes reported to date, an incident photon‐to‐current efficiency of 76% at 400 nm, and high stability over 20 h for PEC water splitting are reported. This work provides an alternative promising prototype for the design and construction of novel heterostructures in robust PEC water splitting applications.     

Ratiometric fluorescent detection of Cu2+ based on dual‐emission ZIF‐8@rhodamine‐B nanocomposites

Zeolitic imidazolate framework‐8 (ZIF‐8) loading rhodamine‐B (ZIF‐8@rhodamine‐B) nanocomposites was proposed and used as ratiometric fluorescent sensor to detect copper(II) ion (Cu²⁺). Scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray powder diffraction, nitrogen adsorption/desorption isotherms and fluorescence emission spectroscopy were employed to characterize the ZIF‐8@rhodamine‐B nanocomposites. The results showed the rhodamine‐B was successfully assembled on ZIF‐8 based on the π‐π interaction and the hydrogen bond between the nitrogen atom of ZIF‐8 and –COOH of rhodamine‐B. The as‐obtained ZIF‐8@rhodamine‐B nanocomposites were octahedron with size about 150–200 nm, had good water dispersion, and exhibited the characteristic fluorescence emission of ZIF‐8 at 335 nm and rhodamine‐B at 575 nm. The Cu²⁺ could quench fluorescence of ZIF‐8 rather than rhodamine‐B. The ZIF‐8 not only acted as the template to assemble rhodamine‐B, but also was employed as the signal fluorescence together with the fluorescence of rhodamine‐B as the reference to construct a novel ratiometric fluorescent sensor to detect Cu²⁺. The resulted ZIF‐8@rhodamine‐B nanocomposite fluorescence probe showed good linear range (68.4 nM to 125 μM) with a low detection limit (22.8 nM) for Cu²⁺ combined with good sensitivity and selectivity. The work also provides a better way to design ratiometric fluorescent sensors from ZIF‐8 and other fluorescent molecules.     

Recent Advancement of p‐ and d‐Block Elements,Single Atoms,and Graphene‐Based Photoelectrochemical Electrodes for Water Splitting

Solar‐assisted photoelectrochemical (PEC) water splitting to produce hydrogen energy is considered the most promising solution for clean, green, and renewable sources of energy. For scaled production of hydrogen and oxygen, highly active, robust, and cost‐effective PEC electrodes are required. However, most of the available semiconductors as a PEC electrodes have poor light absorption, material degradation, charge separation, and transportability, which result in very low efficiency for photo‐water splitting. Generally, a promising photoelectrode is obtained when the surface of the semiconductor is modified/decorated with a suitable co‐catalyst because it increases the light absorbance spectrum and prevents electron–hole recombination during photoelectrode reactions. In this regard, numerous p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes have been widely used as semiconductor/co‐catalyst junctions to boost the performances of PEC overall water splitting. This review enumerates the recent progress and applications of p‐ and d‐block elements, single atoms, and graphene‐based PEC electrodes for water splitting. The focus is placed on fundamental mechanism, efficiency, cells design, and various aspects that contribute to the large‐scale prototype device. Finally, future perspectives, summary, challenges, and outlook for improving the activity of PEC photoelectrodes toward whole‐cell water splitting are addressed.     

Crystalline Ni(OH)2/Amorphous NiMoOx Mixed‐Catalyst with Pt‐Like Performance for Hydrogen Production

The achievement of effective alkaline hydrogen production from water electrolysis is an active field of research. Herein, an integrated electrode composed of crystalline Ni(OH)₂ and amorphous NiMoO_x is fabricated onto nickel foam (denoted as Ni(OH)₂–NiMoO_x/NF). The hydrogen evolution reaction (HER) kinetics are optimized along with phase transformation process during soaking operation. An overpotential of 36 mV to drive 10 mA cm^?2 along with the low Tafel slope of 38 mV dec^?1 reveals the catalyst's excellent HER performance and a Heyrovsky‐step‐controlled HER mechanism. When assembled into a urea‐assisted water electrolyzer, a voltage of 1.42 V can reach 10 mA cm^?2. Further experiments and Fourier transform infrared spectroscopy (FTIR) results illustrate the synergy effect between crystalline and amorphous areas and the optimized water dissociation step. Crystalline Ni(OH)₂ serves as the scissor for water dissociation in an alkali environment to produce H*, while the amorphous NiMoO_x layer serves as the location for H* adsorption and H₂ desorption.     

Cu,Co‐Embedded N‐Enriched Mesoporous Carbon for Efficient Oxygen Reduction and Hydrogen Evolution Reactions

Rational synthesis of hybrid, earth‐abundant materials with efficient electrocatalytic functionalities are critical for sustainable energy applications. Copper is theoretically proposed to exhibit high reduction capability close to Pt, but its high diffusion behavior at elevated fabrication temperatures limits its homogeneous incorporation with carbon. Here, a Cu, Co‐embedded nitrogen‐enriched mesoporous carbon framework (CuCo@NC) is developed using, a facile Cu‐confined thermal conversion strategy of zeolitic imidazolate frameworks (ZIF‐67) pre‐grown on Cu(OH)₂ nanowires. Cu ions formed below 450 °C are homogeneously confined within the pores of ZIF‐67 to avoid self‐aggregation, while the existence of Cu? N bonds further increases the nitrogen content in carbon frameworks derived from ZIF‐67 at higher pyrolysis temperatures. This CuCo@NC electrocatalyst provides abundant active sites, high nitrogen doping, strong synergetic coupling, and improved mass transfer, thus significantly boosting electrocatalytic performances in oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). A high half‐wave potential (0.884 V vs reversible hydrogen potential, RHE) and a large diffusion‐limited current density are achieved for ORR, comparable to or exceeding the best reported earth‐abundant ORR electrocatalysts. In addition, a low overpotential (145 mV vs RHE) at 10 mA cm^?2 is demonstrated for HER, further suggesting its great potential as an efficient electrocatalyst for sustainable energy applications.     

The “Midas Touch” Transformation of TiO2 Nanowire Arrays during Visible Light Photoelectrochemical Performance by Carbon/Nitrogen Coimplantation

Titanium dioxide is a promising photoanode material for water oxidation, but it is substantially limited by its poor efficiency in the visible light range. Herein, an innovative carbon/nitrogen coimplantation method is utilized to realize the “Midas touch” transformation of TiO₂ nanowire (NW) arrays for photoelectrochemical (PEC) water splitting in visible light. These modified golden–yellow rutile TiO₂ NW arrays (C/N‐TiO₂) exhibit remarkably enhanced absorption in visible light regions and more efficient charge separation and transfer. As a result, the photocurrent density of carbon/nitrogen co‐implanted TiO₂ under visible light (>420 nm) can reach 0.76 mA cm^?2, which far exceeds the value of 3 µA cm^?2 seen for pristine TiO₂ nanowire arrays at 0.8 V versus Ag/AgCl. An incident photon to electron conversion efficiency of ≈14.8% is achieved at 450 nm on C/N‐TiO₂ without any other cocatalysts. The ion implantation doping approach, combined with codoping strategies, is proved to be an effective strategy for enhancing the photoelectrochemical conversion and can enable further improvement of the PEC water‐splitting performance of many other semiconductor photoelectrodes.     

Light‐Driven BiVO4–C Fuel Cell with Simultaneous Production of H2O2

Photoelectrochemical (PEC) systems have been researched for decades due to their great promise to convert sunlight to fuels. The majority of the research on PEC has been using light to split water to hydrogen and oxygen, and its performance is limited by the need of additional bias. Another research direction on PEC using light, is to decompose organic materials while producing electricity. In this work, the authors report a new type of unassisted PEC system that uses light, water and oxygen to simultaneously produce electricity and hydrogen peroxide (H₂O₂) on both the photoanode and cathode, which is essentially a light‐driven fuel cell with H₂O₂ as the main product at the two electrodes, meanwhile achieving a maximum power density of 0.194 mW cm^‐2, an open circuit voltage of 0.61 V, and a short circuit current density of 1.09 mA cm^‐2. The electricity output can be further used as a sign for cell function when accompanied by a detector such as a light‐emitting diode (LED) light or a multimeter. This is the first work that shows H₂O₂ two‐side generation with a strict key factors study of the system, with a clear demonstration of electricity output ability using low‐cost earth abundant materials on both sides, which represents an exciting new direction for PEC systems.     

Recent Advances and Emerging Trends in Photo‐Electrochemical Solar Energy Conversion

Photo‐electrochemical (PEC) solar energy conversion offers the promise of low‐cost renewable fuel generation from abundant sunlight and water. In this Review, recent developments in photo‐electrochemical water splitting are discussed with respect to this promise. State‐of‐the‐art photo‐electrochemical device performance is put in context with the current understanding of the necessary requirements for cost‐effective solar hydrogen generation (in terms of solar‐to‐hydrogen conversion efficiency and system durability, in particular). Several important studies of photo‐electrochemical hydrogen generation at p‐type photocathodes are highlighted, mostly with protection layers (for enhanced durability), but also a few recent examples where protective layers are not needed. Recent work with the widely studied n‐type BiVO₄ photoanode is detailed, which highlights the needs and necessities for the next big photoanode material yet to be discovered. The emerging new research direction of photo‐electrocatalytic upgrading of biomass substrates toward value‐added chemicals is then discussed, before closing with a commentary on how research on PEC materials remains a worthwhile endeavor.     

Awakening Solar Water‐Splitting Activity of ZnFe2O4 Nanorods by Hybrid Microwave Annealing

1D zinc ferrite (ZnFe₂O₄) photoanode is fabricated on an F‐doped tin oxide substrate at a low temperature by an all‐solution method. To activate the material for photoelectrochemical water splitting, the hybrid microwave annealing (HMA) is applied with graphite powder as a susceptor. Thus, HMA treatment of ZnFe₂O₄ photoanode synthesized at 550 °C increases the photocurrent density of water oxidation by 15 times. In contrast, the conventional thermal annealing at 800 °C brings only 1.7‐fold increase. The various physical characterizations and hole scavenger photooxidation experiments with H₂O₂ reveal that the post‐HMA treatment anneals the surface defect states and enhances the crystallinity. Hence, HMA treatment is effective to suppress charge‐carrier recombination both on the surface and in the bulk of ZnFe₂O₄ to bring out its latent solar water‐splitting activity.     

General Dimension‐Controlled Synthesis of Hollow Carbon Embedded with Metal Singe Atoms or Core–Shell Nanoparticles for Energy Storage Applications

Metal–organic framework (MOF) derived carbonaceous nanocomposites have recently received enormous interest due to their intriguing physiochemical properties and diverse energy applications. However, there is a lack of general synthetic approaches that can achieve flexible dimension control while manipulating metal dispersion of MOF derived carbon composites. Herein, the authors present an attractive route for the growth of zeolitic imidazolate frameworks (ZIFs) with different dimensions and types of metal nodes that can be further transformed into either core–shell nanoparticles or metal single atoms. The formation of a ZIF‐8 seed layer on ZnO template is identified as the key step, enabling uniform growth of various ZIF materials (e.g., Zn/Co‐ZIF, Zn/Fe‐ZIF, and ZIF‐7) with different dimensions (1D, 2D, and 3D). Simultaneously, this approach avoids free growth of 0D MOF particles and diminishing of the ZnO template. To demonstrate the importance of dimensional control over the growth of ZIF materials for energy application, the 1D and 2D ZnO@ZIF precursors are converted into carbon nanotube and carbon nanoplate, which are decorated with Co/CoS₂ nanoparticles and Fe single atoms, respectively. Two high dimensional carbon nanocomposites deliver significantly enhanced performances compared to their 0D counterparts when employed as the Li‐ion battery anode and bifunctional oxygen electrocatalyst.     

Binary Indium–Zinc Oxide Photoanodes for Efficient Dye‐Sensitized Solar Cells

The benefits of incorporating binary metal‐oxide electrodes en route toward efficient dye‐sensitized solar cells (DSSCs) have recently emerged. The current work aims at realizing efficient indium‐doped zinc oxide based DSSCs by means of enhancing charge transport processes and reducing recombination rates. Electrochemical impedance spectroscopic assays corroborate that low amounts of indium reduce charge transport resistances and increase electron recombination resistances. The latter are in concert with a remarkable enhancement of the charge collection efficiency from 33% to 83% for devices with ZnO and In₁₅Zn₈₅O photoanodes, respectively. Going beyond 15 mol% of indium, an effective electron trapping increases the charge transport resistance and, in turn, dramatically reduces charge collection efficiency. Upon implementing In₁₅Zn₈₅O into an electron cascade photoanode architecture featuring an In₁₅Zn₈₅O bottom layer and a ZnO top layer, a device efficiency of 5.77% and a significantly high current density of 20.4 mA cm^?2 in binary ZnO DSSCs are achieved.     

Low‐Overpotential Electrocatalytic Water Splitting with Noble‐Metal‐Free Nanoparticles Supported in a sp3 N‐Rich Flexible COF

Covalent organic frameworks (COFs) are crystalline organic polymers with tunable structures. Here, a COF is prepared using building units with highly flexible tetrahedral sp³ nitrogens. This flexibility gives rise to structural changes which generate mesopores capable of confining very small (<2 nm sized) non‐noble‐metal‐based nanoparticles (NPs). This nanocomposite shows exceptional activity toward the oxygen‐evolution reaction from alkaline water with an overpotential of 258 mV at a current density of 10 mA cm^?2. The overpotential observed in the COF‐nanoparticle system is the best in class, and is close to the current record of ≈200 mV for any noble‐metal‐free electrocatalytic water splitting system—the Fe–Co–Ni metal‐oxide‐film system. Also, it possesses outstanding kinetics (Tafel slope of 38.9 mV dec^?1) for the reaction. The COF is able to stabilize such small‐sized NP in the absence of any capping agent because of the COF–Ni(OH)₂ interactions arising from the N‐rich backbone of the COF. Density‐functional‐theory modeling of the interaction between the hexagonal Ni(OH)₂ nanosheets and the COF shows that in the most favorable configuration the Ni(OH)₂ nanosheets are sandwiched between the sp³ nitrogens of the adjacent COF layers and this can be crucial to maximizing their synergistic interactions.     

Triblock‐Terpolymer‐Directed Self‐Assembly of Mesoporous TiO2: High‐Performance Photoanodes for Solid‐State Dye‐Sensitized Solar Cells

A new self‐assembly platform for the fast and straightforward synthesis of bicontinuous, mesoporous TiO₂ films is presented, based on the triblock terpolymer poly(isoprene ‐ b ‐ styrene ‐ b ‐ ethylene oxide). This new materials route allows the co‐assembly of the metal oxide as a fully interconnected minority phase, which results in a highly porous photoanode with strong advantages over the state‐of‐the‐art nanoparticle‐based photoanodes employed in solid‐state dye‐sensitized solar cells. Devices fabricated through this triblock terpolymer route exhibit a high availability of sub‐bandgap states distributed in a narrow and low enough energy band, which maximizes photoinduced charge generation from a state‐of‐the‐art organic dye, C220. As a consequence, the co‐assembled mesoporous metal oxide system outperformed the conventional nanoparticle‐based electrodes fabricated and tested under the same conditions, exhibiting solar power‐conversion efficiencies of over 5%.