Entire Solar Spectrum Research Articles

Photocatalytic seawater splitting by Earth-abundant catalysts: metal-semiconductor metamaterials made of plasmonic magnesium diboride and transitional metal dichalcogenides.

Metal-semiconductor metamaterials hold great promise for photocatalytic water splitting due to their excellent light harvesting in a broad spectral range as well as efficient charge carrier generation and transfer. In majority of such metamaterials, semiconductors are used to initiate the water splitting reaction, while their metal counterparts are employed to improve light harvesting through plasmonic effects. Here, we describe for the first time an exceptional reversed case of metal-semiconductor photocatalysts in which metals are used to initiate the water splitting reaction and semiconductors are employed to improve light harvesting through blackbody effect and serve as co-catalysts. The studied photoanodes are made of non-noble plasmonic MgB2 combined with transition metal dichalcogenides (TMDCs). The plasmonic resonances of the MgB2 component contribute to field confinement, plasmon-exciton coupling, and hot-electron transfer providing an enhancement of photoactivity in the entire solar spectrum capable of water splitting. The TMDC component provides impedance matching and enhances light absorption by the metal catalyst. We demonstrate seawater splitting with MgB2-TMDCs photoanodes attaining current densities of ~ 3 mA⋅cm-2 at solar radiation. The overall efficiency of hydrogen production in seawater splitting by sunlight with the help of the studied photoanodes is 3% at bias voltage of Vbias = 0.3 V.

Solar evaporation of liquid marbles with composite nanowire arrays

Solar interfacial evaporation is a sustainable technology to produce fresh water. The synergistic realization of broadband light absorption and good thermal insulation is crucial to improving the thermal efficiency. Here, we propose a new structure over the surface of liquid marbles, which via nanowire arrays assembled with composite nanomaterials (Fe3O4/CNT nanoparticles) to enhance the evaporation efficiency. The composite materials can effectively absorb light across the entire solar spectrum. Multiple reflections of light over nanowire array further improve light absorption. The narrow spaces and local particle aggregation of the nanowire array enhance thermal insulation to improve the evaporation efficiency. A series of experiments were conducted to verify the concept. The results showed that liquid marbles with upward Fe3O4/CNT nanowire arrays (Fe3O4/CNT-ULM) enhance the light harvesting ability and thermal insulation. Fe3O4/CNT-ULM at a volume ratio 1:2 provides the highest evaporation rate of 12.25 μg/s, which is about 1.16 and 1.53 times higher than that of Fe3O4 and CNT, respectively. Numerical analysis further illustrates that the combination of composite materials and nanowire arrays enhances concentration of electromagnetic field and heat at the air/water interfaces. This promotes rapid evaporation at the thermal boundary region, which has important implications for the structure design of solar interfacial evaporator.

Efficiency limits of concentrated solar thermophotonic converters under realistic conditions: The impact of nonradiative recombination and temperature dependence

A concentrated solar thermophotonic converter (CSTC) that efficiently harvests the entire solar spectrum under non-ideal conditions is proposed. This device includes an optical concentrator, a solar absorber, a GaAs light-emitting diode (LED) on the hot side, and an InP photovoltaic (PV) cell on the cold side. The electric power generated by the PV cell is utilized to positively bias the heated LED, resulting in a substantial increase in LED emission power. A comprehensive theoretical model is developed to accurately predict the output electrical performance and overall energy conversion efficiency of the CSTC device, especially considering the impact of the nonradiative recombination and temperature dependence. The calculated results show that when the solar concentrating factor is 30, and the LED and PV cell voltages are 0.989 V and 1.13 V, respectively, the overall peak efficiency can reach 12.8% and the corresponding output power density is 384 mW cm−2, achieving performance metrics nearly 4 orders of magnitude higher than solar thermophotovoltaics (TPV). Additionally, increasing the solar concentration ratio and decreasing the thickness of the semiconductor materials can further improve the overall output performance. This work reveals that CSTC offers several advantages over solar TPV, including more efficient conversion of narrow-spectrum electroluminescence, higher radiated power from the LED emitter, and the ability to operate at lower solar concentrations and lower costs.

Assembled Wood-Polyester Fabric-Hydrogel Janus Evaporator for Sustainable Seawater Desalination.

Solar-driven interfacial evaporation technology is a novel and efficient desalination process that helps alleviate the global shortage of freshwater resources. We developed a Janus evaporator assembled from cotton hydrogel, hydrophilic polyester fabric (PF), and Hydrophobic Wood (PW). By doping graphene oxide and TiO2 as light-absorbing materials within the hydrogel, we achieved a high absorptivity of over 90% across the entire solar spectrum. The hydrophilically modified PF, combined with the PW substrate, provided robust water transport and reduced thermal losses. Subsequent optical path simulations using TracePro74 software verified that the sawtooth light-trapping design of the wood substrate increased multiple light reflections and absorption (compared to a flat structure), enhancing light absorption capabilities. The sawtooth interface also enlarged the evaporation area, further boosting evaporation performance. The cleverly designed evaporator exhibited an evaporation rate of 1.722 kg m-2 h-1 and an efficiency of 83.1% under 1 sun irradiation. Additionally, after applying polydimethylsiloxane to the single surface of the photothermal hydrogel for low surface energy treatment, the resulting Janus structure demonstrated asymmetric wettability that prevented salt ions from accumulating on the irradiated interface. After 8 h of continuous evaporation in saline water (10 wt %), only slight salt crystallization occurred at the edges. The evaporator maintained long-term stability during a 15 day cyclic test, and the produced freshwater fully met the relevant drinking water standards. The components of the evaporator are characterized by simple fabrication, low cost, and eco-friendliness, offering significant application potential in the global context of energy conservation and emission reduction initiatives.

Strong absorption of silica over full solar spectrum boosted by interfacial junctions and light–heat–storage of Mg(OH)2–(CrOx–SiO2)

Strong absorption of near-infrared (NIR) light is essential for efficient solar energy applications. NIR absorption primarily depends on the surface plasmon resonance of incident light with free charge carriers (FCCs). We demonstrated that S-scheme interfacial junctions (IJs) can substantially enhance FCC density, light-harvesting, photocurrent intensity, long lifetime of the charge carriers and photothermal effects, paving a way for novel light-material design. Abundant S–scheme IJs are constructed in CrOx–SiO2 nanoparticles, which increase the FCCs outstandingly and enhance light absorption exceptionally over the entire solar spectrum. IJs’ construction enables silica to harvest solar energy strongly. Doped with multifunctional CrOx–SiO2 nanoparticles, the photothermal-dehydration conversion and the stored heat of Mg(OH)2 can be improved by 7.0- and 5.1-times upon 30-min irradiation, respectively. The reversibility of the photothermal charge–discharge cycles of Mg(OH)2 improves 19.3 times. The thermal-storage kinetics is substantially improved owing to the reduction of the dehydration activation energy (−15.2 %). Mg(OH)2–CrOx–SiO2 composite is an excellent one-step system of light–heat–storage.

Optimization of InGaN-based solar cells by numerical simulation: Enhanced efficiency and performance analysis

The development of efficient solar cells is limited by the inability of the materials to absorb light from the entire solar spectrum. InGaN solar cells have become promising, due to the broad bandgap coverage of the solar spectrum from 0.7 eV to 3.42 eV. The performance of InGaN devices is simulated using SCAPS-1D software. The impacts of layer thickness and defect density on the performance of p-n and p-p-n junction InGaN solar cells were investigated, including holistic optimization of power conversion efficiency and quantum efficiency. A notable observation was the improvement in conversion efficiency with rising indium content, peaking at 23.8 % for In0.6Ga0.4N. For p-p-n junction cells, a thicker p-layer plus an additional thin top p-layer with a larger bandgap proved advantageous. The n-layer defect density in p-n junction cells showed minimal effects on open-circuit voltage and fill factor but reduced short-circuit current and efficiency as it increased. Conversely, the p-layer defect density influenced performance only at high densities beyond 1016 cm−3, while for p-p-n junctions, the top p-layer’s defect density had minimal impact. The optimized designs for both p-n and p-p-n junction cells, incorporating graded bandgaps, achieved optimal conversion efficiencies of 33.89 % and 34.07 %, respectively. The p-p-n design showed an enlarged high-efficiency area for suitable indium concentrations, offering broader indium concentration tuning possibilities and better lattice constant tuning. Quantum efficiency evaluations show the differences of defect densities and thicknesses across specific wavelength intervals, reaffirming the potential for strategic cell design choices.

Bioinspired multiscale hierarchical structure enables solar-thermal conversion for low-temperature aqueous electrochromic device

Solar-thermal conversion can mitigate the inadequate electrochemical performance in extreme cold environment for aqueous electrochromic devices (AEDs). However, the limited intrinsic absorptance of electrochromic materials impedes a satisfying solar-thermal conversion. Herein, bioinspired by the Paradisaeidae’s super black feathers, multiscale hierarchical structure is purposely made to compose of WO3-x nanowires (WNWs) and silver nanowires (AgNWs), where WNWs are grown on AgNWs in different orientations (denoted as WAg). Our ray tracing simulation reveals its underlying absorption mechanism, demonstrating both an increased optical path and a concentrated energy distribution. Comparably, the WAg-AED exhibits much enhanced absorption (87.0 vs. 68.5 % across the entire solar spectrum) and a broader surface temperature change (51.2 vs. 39.7 °C within 8 min) under 1 solar illumination. This leads to a rapid recovery of electrochromic/electrochemical performance even conducted at −20 °C. Notably, upon irradiation for 12 min, the areal capacities of WAg-AED at 0.5mA cm−2 increase by 3.8 and 1.7 times, when compared to the device operating at −20 °C and room temperature, respectively. The WAg-AED establishes a close connection between the photo-thermal conversion and electrochemistry, proving a new pathway in the development of sustainable electronics.

An updated review and perspective on efficient hydrogen generation via solar thermal water splitting

AbstractSolar thermal water splitting (STWS) produces renewable (or green) hydrogen from water using concentrated sunlight. Because STWS utilizes energy from the entire solar spectrum to drive the reduction–oxidation (redox) reactions that split water, it can achieve high theoretical solar‐to‐hydrogen efficiencies. In a two‐step STWS process, a metal oxide that serves as a redox mediator is first heated with concentrated sunlight to high temperatures (T >1000°C) to reduce it and evolve oxygen. In the second step, the reduced material is exposed to steam to reoxidize it to its original oxidation state and produce hydrogen. Various aspects of this process are comprehensively reviewed in this work, including the reduction and oxidation chemistries of active materials considered to date, the solar reactors developed to facilitate the STWS reactions, and the effects of operating conditions—including the recent innovation of elevated oxidant pressure—on efficiency. To conclude the review, a perspective on the future optimization of STWS is provided.This article is categorized under: Sustainable Energy > Solar Energy Emerging Technologies > Hydrogen and Fuel Cells Emerging Technologies > New Fuels

Multiphysics modeling tool for photovoltaic-thermoelectric hybrid devices integrating a photothermal interface

Photovoltaic-thermoelectric hybrid devices aim at harvesting the entire solar spectrum via both direct photovoltaic conversion and subsequent thermoelectric conversion of the heat generated in the solar cell. One emerging strategy to improve their efficiency is to implement a photothermal interface between the photovoltaic cell and the thermoelectric module. Modeling such a complex system (photovoltaic cell, photothermal interface and thermoelectric generator) to design an optimal architecture is a challenging task, as it requires to take into account a large number of parameters in a multi-layered system, as well as the coupling between optical, thermal and electrical effects. To do so, we present here a multiphysics tool to predict the temperature distribution and power output of hybrid devices integrating a photothermal interface. Our model shows a good quantitative agreement with previous theoretical and experimental works from the literature using limited material parameters. We discuss the need for additional parameters for accurate modeling of experimental devices. We envision that our multiphysics modeling tool will be key for the design of optimal photothermal interfaces for efficient photovoltaic-thermoelectric hybrid devices.

Materials Advances in Photocatalytic Solar Hydrogen Production: Integrating Systems and Economics for a Sustainable Future.

Photocatalytic solar hydrogen generation, encompassing both overall water splitting and organic reforming, presents a promising avenue for green hydrogen production. This technology holds the potential for reduced capital costs in comparison to competing methods like photovoltaic-electrocatalysis and photoelectrocatalysis, owing to its simplicity and fewer auxiliary components. However, the current solar-to-hydrogen efficiency of photocatalytic solar hydrogen production has predominantly remained low at ≈1-2% or lower, mainly due to curtailed access to the entire solar spectrum, thus impeding practical application of photocatalytic solar hydrogen production. This review offers an integrated, multidisciplinary perspective on photocatalytic solar hydrogen production. Specifically, the review presents the existing approaches in photocatalyst and system designs aimed at significantly boosting the solar-to-hydrogen efficiency, while also considering factors of cost and scalability of each approach. In-depth discussions extending beyond the efficacy of material and system design strategies are particularly vital to identify potential hurdles in translating photocatalysis research to large-scale applications. Ultimately, this review aims to provide understanding and perspective of feasible pathways for commercializing photocatalytic solar hydrogen production technology, considering both engineering and economic standpoints.

Plasmonic Near-Infrared-Response S-Scheme ZnO/CuInS2 Photocatalyst for H2O2 Production Coupled with Glycerin Oxidation.

Solar fuel synthesis is intriguing because solar energy is abundant and this method compensates for its intermittency. However, most photocatalysts can only absorb UV-to-visible light, while near-infrared (NIR) light remains unexploited. Surprisingly, the charge transfer between ZnO and CuInS2 quantum dots (QDs) can transform a NIR-inactive ZnO into a NIR-active composite. This strong response is attributed to the increased concentration of free charge carriers in the p-type semiconductor at the interface after the charge migration between ZnO and CuInS2, enhancing the localized surface plasmon resonance (LSPR) effect and the NIR response of CuInS2. As a paradigm, this ZnO/CuInS2 heterojunction is used for H2O2 production coupled with glycerin oxidation and demonstrates supreme performance, corroborating the importance of NIR response and efficient charge transfer. Mechanistic studies through contact potential difference (CPD), Hall effect test, and finite element method (FEM) calculation allow for the direct correlation between the NIR response and charge transfer. This approach bypasses the general light response issues, thereby stepping forward to the ambitious goal of harnessing the entire solar spectrum.

Hierarchical Gradient Structural Porous Metamaterial with Selective Spectral Response for Daytime Passive Radiative Cooling

AbstractPorous photonic structures have greatly advanced large‐scale radiative cooling application owing to its satisfying optical properties, easy‐designation, and low cost. However, current reported porous radiative cooling materials mainly focuses on uniform or random pore distribution structure, which failed to achieve precise spectrum control for sunlight and mid‐infrared light, thereby weakening the radiative cooling performance. Herein, gradient structural porous metamaterials (GSPMs) are proposed and successfully constructed for maximizing cooling effectiveness based on step‐by‐step freeze‐casting technology. The designed GSPMs with gradient micro‐nano porous structure can wide‐range scatter entire solar spectrum while possess gradual refractive index transition to increase air‐medium interface absorption at mid‐infrared regions. Notably, solar reflectivity and mid‐infrared emissivity of GSPMs reach 97.3% and 97.6%, achieving maxinum cooling temperature of 8.7 °C and net cooling power of 94.1 W m−2, presenting a higher cooling effect than random porous materials. Moreover, GSPMs enable achieve compatibility with color aesthetic and cooling superiorities due to selective spectra response behavior, as well as can be applied in building materials, realizing efficient energy saving and CO2 emission reduction. This work proposed gradient porous structure can achieve highly efficient daytime radiative cooling, offering new possibilities in the structure design of next‐generation porous radiative cooling materials.

Solar-Driven Biomass Reforming for Hydrogen Generation: Principles, Advances, and Challenges.

Hydrogen (H2) has emerged as a clean and versatile energy carrier to power a carbon-neutral economy for the post-fossil era. Hydrogen generation from low-cost and renewable biomass by virtually inexhaustible solar energy presents an innovative strategy to process organic solid waste, combat the energy crisis, and achieve carbon neutrality. Herein, the progress and breakthroughs in solar-powered H2 production from biomass are reviewed. The basic principles of solar-driven H2 generation from biomass are first introduced for a better understanding of the reaction mechanism. Next, the merits and shortcomings of various semiconductors and cocatalysts are summarized, and the strategies for addressing the related issues are also elaborated. Then, various bio-based feedstocks for solar-driven H2 production are reviewed with an emphasis on the effect of photocatalysts and catalytic systems on performance. Of note, the concurrent generation of value-added chemicals from biomass reforming is emphasized as well. Meanwhile, the emerging photo-thermal coupling strategy that shows a grand prospect for maximally utilizing the entire solar energy spectrum is also discussed. Further, the direct utilization of hydrogen from biomass as a green reductant for producing value-added chemicals via organic reactions is also highlighted. Finally, the challenges and perspectives of photoreforming biomass toward hydrogen are envisioned.

Harnessing intrinsic electric fields in 2D Janus MoOX (X=S, Se, and Te) monolayers for enhanced photocatalytic hydrogen evolution

Two-dimensional (2D) Janus monolayers, distinguished by their intrinsic vertical electric fields, emerge as highly efficient and eco-friendly materials for advancing the field of hydrogen evolution reactions (HER). In this study, we explore, for the first time, the potential viability of the oxygenation phase of two-dimensional Janus transition metal dichalcogenides MoOX (X = S, Se, and Te) monolayers as an exceptionally efficient photocatalyst for hydrogen production. Based on first-principles computations, we demonstrate that all three monolayers exhibit semiconductor behavior, characterized by a band gap ranging from 0.66 to 1.55 eV. This narrow band gap renders the proposed materials highly efficient at absorbing light within the visible region. Excitingly, the introduction of an electrostatic potential difference ΔΦ has granted us the ability to surpass the conventional bandgap limit (Eg≥1.23). Consequently, all monolayers exhibit favorable band alignment with respect to the vacuum level. Moreover, the calculated solar-to-hydrogen efficiency for the envisaged monolayer exceeds the established theoretical limit. Particularly, the MoOTe monolayer emerges as an infrared-light-driven photocatalyst, demonstrating a remarkable solar-to-hydrogen efficiency limit of up to 25,21% when considering the entire solar spectrum. A thorough examination of the Gibbs free energy differences across these monolayers has revealed that the values during the oxygenation phase are significantly smaller and approach the optimum, in contrast to the parental two-dimensional Janus transition metal dichalcogenides. Our results conclusively establish that the proposed materials exhibit exceptional efficiency as photocatalysts for hydrogen evolution reactions. Notably, their efficacy is demonstrated even in the lack of co-catalysts or sacrificial agents.

Strong absorption of (Mn2O3)3CuSiO3 with Jahn–Teller elongation and direct photothermal storage of (Mn2O3)3CuSiO3–Mg(OH)2

To improve photon harvesting, we demonstrated that Jahn–Teller defects can efficiently reduce the band gap and increase the carrier density, which significantly intensify light harvesting and widen the absorption band. This may be an effective method for designing solar materials. The substitution of Mn2+ with Jahn–Teller active Cu2+ leads to quasi-metallic (Mn2O3)3CuSiO3 nanoparticles with a high concentration of charge carriers, displaying intense absorption in entire solar spectrum. Silicates may represent a new type of photon harvesting material. Mg(OH)2 powder coated by Cu-braunite shows a 150 % increase in photothermal temperature, a tenfold improvement in photothermal-dehydration conversion and a 15.8-fold increase in the reversibility of 30 cycles of heat storage and release. This material may be practicable for directly harvesting solar energy and storing thermoenergy. Jahn–Teller effects are effective for tuning photon harvesting.

Silver doped anatase nanocomposite: a novel photocatalyst with advanced activity under visible light for waste-water treatment

Anatase is a universal semiconductor photocatalyst; however, its wide band-gap energy limits its entire solar spectrum absorption to only 5%. Anatase could be activated in the visible region via nobel metal deposition. This study reports on the facile synthesis of colloidal mono-dispersed anatase nanoparticles of 5 nm particle size via hydrothermal synthesis. Nobel metals (Silver, Nickel) were deposited on colloidal anatase surface. The photocatalytic activities of Ag–TiO2, and Ni–TiO2 were investigated for the degradation of basic fuchsin dye. Ag–TiO2 nanocomposite demonstrated enhanced adsorption activity in dark, as well as superior photocatalytic. Ag–TiO2 nanocomposite demonstrated enhanced removal efficiency by 70.8% under visible irradiation to virgin anatase. Ag–TiO2 nanocomposite demonstrated enhanced oxygen-lattice with low binding energy using XPS analysis. Ag–TiO2 experienced band gap energy of 2.35 eV compared with 3.2 eV for virgin anatase; this feature could secure enhanced solar absorption. Ag–TiO2 demonstrated excellent photo-degradation efficiency of 88% with 0.3% H2O2 under visible light. Deposited silver could catalyze H2O2 decomposition and could promote free radical generation; Ag–TiO2 nanocomposite is a promising photocatalyst for wastewater treatment applications.

Investigation of graphene-perovskite integration for enhanced absorption of solar thermal absorber for industrial heating applications

Advanced materials are critical for enhancing the efficiency of solar absorbers. Hence, the present study looks at the unique interaction between graphene and perovskite materials, a combination that has the potential to change the landscape of solar energy harvesting. The Graphene–Perovskite Integrated Solar Absorber (GPISA) structure harvests more than 98 % in UV and VIS regions ranging from 200 nm and goes up to 4000 nm of the solar spectrum using the Finite Element Method (FEM). Not only does it boast a broader absorption range from 200 to 4000 nm, covering virtually the entire solar spectrum, but it also achieves an impressive average absorption of 95.50 %. Additionally, the comprehensive analysis of its performance, encompasses optimized parameterization, exhaustive mapping of electric and magnetic field intensities, and in-depth investigation of both transverse magnetic (TM) and transverse electric (TE) field behaviors. This correlates to a weighted absorption rate of more than 97 % in the AM1.5 solar spectrum, as well as endurance to varied incoming angles (0°–80°) without considerable absorption loss, making it suitable for real-world direct sunlight absorptance. The GPISA is significantly more cost-effective due to its 3240 nm thickness. Overall, GPISA's exceptional combination of broad absorption, high efficiency, and compact design firmly positions it as a frontrunner in the advancement of efficient, high-performance solar energy harvesting. GPISA has efficient uses in solar induction systems as well as solar air, water heating, and other industrial heating applications.

Real‐time thermal performance investigation of a thermal energy storage integrated direct absorption solar collector under tropical climate

AbstractIn the last two decades, metallic particles of nano sizes (~10−9 m) have been tested profoundly in volumetric absorption solar collectors (VASC) due to their excellent optical properties and broadband absorption in the entire solar spectrum. However, very limited studies are available for understanding the performance of integrated energy storage VASC systems using nanofluids. For the experimental work presented here, a hybrid nanofluid of gold nanoparticles in Azadirachta indica leaves extract has been synthesized by chemical route. The prepared hybrid nanofluid has shown good absorption in 400 to 700 nm wavelength range and hence achieved high photo‐thermal conversion efficiency for tested VASC system. Furthermore, commercially available paraffin wax is used as a phase change material (PCM) in thermal energy storage (TES) and further integrated with VASC to analyze the thermal performance of the system even after sunshine hours. The real‐time experiments were conducted using different working fluids, and at three mass flow rates, that is, 0.008 kg/s, 0.016 kg/s, and 0.033 kg/s, respectively, during mild winter days in the tropical climate of India. The study revealed a photo‐thermal efficiency enhancement of about 17.1% when hybrid heat transfer fluid was used in the VASC system with TES as compared to base fluid water but without TES. During the heating period, the maximum thermal gain of the hybrid nanofluid was observed to be about 15°C higher than the ambient temperature at mass flow rate of 0.033 kg/s. Thermal efficiency enhancement of about 23.8%, 24%, and 24.1% was observed with hybrid nanofluid compared to base fluid water at a mass flow rate of 0.008 kg/s, 0.016 kg/s, and 0.033 kg/s, respectively, when PCM was kept inside the tank. Furthermore, a maximum zero loss efficiency of 83.8% was estimated at an optimal mass flow rate of 0.033 kg/s for the TES‐integrated VASC system.

A strategy of Co doping in MgO to significantly improve the performance of solar-driven thermocatalytic CO2 reduction on Ru/Co-MgO

Dry reforming of CH4 (DRM) driven solely by solar light provides an attractive strategy for solving energy shortages and global warming. The strategy faces two challenges: so far, high fuel productivity and solar-to-fuel efficiency (η) can only be realized at high solar intensities (usually more than 192 kW m−2). Furthermore, coking side reactions are more favorable in thermodynamically, which can lead to catalyst deactivation. Herein, a new nanocomposite of Ru nanoparticles (NPs) loaded on Co-doped MgO with reactive oxygen species and a strong optical absorption throughout the entire solar spectrum (Ru/Co-MgO) is prepared. At relatively low solar intensity (73.2 kw m−2), the solar-driven DRM on Ru/Co-MgO achieves high production rates of CO (rCO, 80.01 mmol g-1catalyst min−1) and H2 (rH2, 62.31 mmol g-1catalyst min−1) with larger η of 26.1 %, which shows an increase of 1.3-fold in rCO, rH2 and η, while a 65-fold decrease in coking rate (rC) compared to a reference catalyst of Ru and Co NPs loaded on MgO (RuCo/MgO). The significant improvement in the catalytic performance stems from the involvement of reactive oxygen (–Co–O–Mg–) in Co-MgO for the oxidation of C* species as a rate-determining step of DRM, which enhances the catalytic activity and significantly inhibits coking. Additionally, the light not only promotes the reactions both of DRM on Ru NPs and strongly adsorbed CO2 on Co-MgO with C* species at the Ru/Co-MgO interface, but also facilitates the dissociation of CO2 adsorbed on the oxygen vacancies of Ru/Co-MgO into CO, thus accelerating the synergistic effect between Ru NPs and Co-MgO.

Dual-plasmonic Au@Cu7S4 yolk@shell nanocrystals for photocatalytic hydrogen production across visible to near infrared spectral region

Near infrared energy remains untapped toward the maneuvering of entire solar spectrum harvesting for fulfilling the nuts and bolts of solar hydrogen production. We report the use of Au@Cu7S4 yolk@shell nanocrystals as dual-plasmonic photocatalysts to achieve remarkable hydrogen production under visible and near infrared illumination. Ultrafast spectroscopic data reveal the prevalence of long-lived charge separation states for Au@Cu7S4 under both visible and near infrared excitation. Combined with the advantageous features of yolk@shell nanostructures, Au@Cu7S4 achieves a peak quantum yield of 9.4% at 500 nm and a record-breaking quantum yield of 7.3% at 2200 nm for hydrogen production in the absence of additional co-catalysts. The design of a sustainable visible- and near infrared-responsive photocatalytic system is expected to inspire further widespread applications in solar fuel generation. In this work, the feasibility of exploiting the localized surface plasmon resonance property of self-doped, nonstoichiometric semiconductor nanocrystals for the realization of wide-spectrum-driven photocatalysis is highlighted.