Photocatalysis has been invariably considered as an unselective process (especially in water) for a fairly long period of time, and the investigation on selective photocatalysis has been largely neglected. In recent years, the field of selective photocatalysis is developing rapidly and now extended to several newer applications. This review focuses on the overall strategies which can improve the selectivity of photocatalysis encompassing a wide variety of photocatalysts, and modifications thereof, as well as the related vital processes of industrial significance such as reduction and oxidation of organics, inorganics, and CO transformation. Comprehensive and successful strategies for enhancing the selectivity in photocatalysis are abridged to reinvigorate and stimulate future investigations. In addition, nonsemiconductor type photocatalysts, such as Ti-Si molecular sieves and carbon quantum dots (CQDs), are also briefly appraised in view of their special role in special selective photocatalysis, namely epoxidation reactions, among others. In the end, a summary and outlook on the challenges and future directions in the research field are included in the comprehensive review.

Element doping has been extensively attempted to develop visible-light-driven photocatalysts, which introduces impurity levels and enhances light absorption. However, the dopants can also become recombination centers for photogenerated electrons and holes. To address the recombination challenge, we report a gradient phosphorus-doped CdS (CdS-P) homojunction nanostructure, creating an oriented built-in electric-field for efficient extraction of carriers from inside to surface of the photocatalyst. The apparent quantum efficiency (AQY) based on the cocatalyst-free photocatalyst is up to 8.2% at 420 nm while the H evolution rate boosts to 194.3 μmol·h·mg, which is 58.3 times higher than that of pristine CdS. This concept of oriented built-in electric field introduced by surface gradient diffusion doping should provide a new approach to design other types of semiconductor photocatalysts for efficient solar-to-chemical conversion.

Infrared light, more than 50% of the solar light energy, is long‐termly ignored in the photocatalysis field due to its low photon energy. Herein, infrared‐light‐responsive photoinduced carriers driver is first constructed taking advantage of pyroelectric effect for enhancing photocatalytic hydrogen evolution. In order to give full play to its role, the photocatalytic reaction is localized on the surface and interface of the composite based on a new semi‐immersion type heat collected photocatalytic microfiber system. The system is consisted of distinctive pyroelectric substrate poly(vinylidene fluoride‐co‐hexafluropropylene (PVDF‐HFP), typical photothermal material carbon nanotube (CNT), and representative photocatalyst CdS. The transient photocurrent, electrochemical impedance spectroscopy, time‐resolved photoluminescence and pyroelectric potential characterizations indicate that the infrared‐light‐responsive carriers driver significantly promotes the photogenerated charge separation, accelerates carrier migration, and prolongs carrier lifetime. The photocatalytic hydrogen evolution efficiency is remarkably improved more than five times with the highest average apparent quantum yield of 16.9%. It may open up new horizons to photocatalytic technology for the more efficient use of infrared light.

Double-shell-structured β-NaYF4:Yb(3+),Tm(3+)/Er(3+)@SiO2@TiO2 upconversion photocatalysts have been successfully synthesized by a simple hydrothermal method. It is found that the double-shell-structured photocatalyst consists of uniform β-NaYF4:Yb(3+),Tm(3+)/Er(3+) nanocrystals, SiO2 as the media shell, and anatase TiO2 nanocrystals exposed with the high-reactive {001} facets as the outer shell. The TiO2 shell is modified to absorb both the UV and visible light in order to make sufficient use of the upconverted light from β-NaYF4:Yb(3+),Tm(3+)/Er(3+) for photocatalysis. Effective energy transfer from β-NaYF4:Yb(3+),Tm(3+)/Er(3+) to TiO2 and its importance are confirmed. The photocatalytic activity in the degradation of Rhodamine B (RhB) under the near-infrared (NIR) (980 nm laser) irradiation suggests that the NIR-driven photocatalytic activity of the double-shell-structured photocatalyst is significantly dependent on the properties of the upconversion materials and the irradiated NIR power density. Moreover, the NIR-driven photocatalyst shows stable photocatalytic degradation of RhB in the recycled tests. This study suggests a promising system and a new insight to understand the application of appropriate upconversion materials to effectively utilize the NIR for photocatalytic applications of TiO2-based photocatalysts, which may advance the application of solar energy in the future.

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